MXPA01001317A - Uracil compounds and their use. - Google Patents

Uracil compounds and their use.

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Publication number
MXPA01001317A
MXPA01001317A MXPA01001317A MXPA01001317A MXPA01001317A MX PA01001317 A MXPA01001317 A MX PA01001317A MX PA01001317 A MXPA01001317 A MX PA01001317A MX PA01001317 A MXPA01001317 A MX PA01001317A MX PA01001317 A MXPA01001317 A MX PA01001317A
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Mexico
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alkyl
compound
chloro
carbon atoms
fluoro
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MXPA01001317A
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Spanish (es)
Inventor
Tohyama Yoshitomo
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Sumitomo Chemical Co
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Publication of MXPA01001317A publication Critical patent/MXPA01001317A/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/69—Two or more oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/70—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pyridine Compounds (AREA)

Abstract

The present invention relates to an uracil compound of the formula °I°: °wherein, Q-R3 represents a R3-substituted group of a 5-membered or 6-membered heterocyclic ring having one or two nitrogen atoms selected from the group consisting of moieties represented in the specification (wherein this heterocyclic ring may be substituted with at least one kind of substituent, Y represents oxygen, sulfur, imino or C1 to C3 alkylimino, R1 represents C1 to C3 alkyl or C1 to C3 haloalkyl, R2 represents C1 to C3 alkyl, R3 represents carboxy C1 to C6 alkyl, C1 to C6 alkoxycarbonyl C1 to C6 alkyl, OR7, SR8, N(R9)R10 or the like, X1 represents halogen, cyano, thiocarbamoyl or nitro, X2 represents hydrogen or halogen. äwherein, each of R7, R8 and R10 independently represents carboxy C1 to C6 alkyl, C1 to C6 alkoxycarbonyl C1 to C6 alkyl, C1 to C6 haloalkoxycarbonyl C1 to C6 alkyl, or the like, and R9 represents hydrogen or C1 to C6 alkyl ü °. The present compound has an excellent herbicidal activity.

Description

COMPOSITIONS OF URACIL AND USE OF THEMSELVES FIELD OF THE INVENTION The present invention relates to uracil.Ó compounds and to the use thereof. An object of the present invention is to provide compounds having excellent herbicidal activity.
BACKGROUND OF THE INVENTION Currently, a batch of herbicides are available and are used, however, since there are many kinds of weeds or weeds to be controlled and the generation of them varies over a long period, there is a requirement a herbicide which has a greater herbicidal effect, has a wide range of herbicidal spectrum, and does not cause phytotoxicity on crops. USP 4,859,229, WO 92/11244, WO97 / 01541, WO97 / 05116, WO98-41093 and the like descri. that certain classes of phenyluracil compounds have REF activity. DO NOT. 126888 herbicide, however, these phenyluracil compounds do not have sufficient capacities as a herbicide.
DESCRIPTION OF THE INVENTION The present inventors have studied intensively to find a compound having excellent herbicidal activity, and as a result, find that uracil compounds of the following formula [I] have excellent herbicidal activity, leading to the termination of the present invention. Primarily, the present invention provides uracil compounds of the formula [I] (later described, referred to as the present compound); [wherein, Q-R3 represents a group substituted on R3 of a 5- or 6-membered heterocyclic ring having one or two nitrogen atoms selected from the group consisting of portions represented by the following formula s (wherein, this heterocyclic ring can be substituted with at least one class of substituent selected from the group consisting of halogen, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 atoms carbon, haloalkenyl of 2 to 6 carbon atoms, alkynyl of 2 to 6 carbon atoms, haloalkynyl of 2 to 6 carbon atoms, Cl to C6 alkoxy Cl to C6 alkyl, alkoxy of 1 to 6 carbon atoms, haloalkoxy from 1 to 6 carbon atoms, Cl to C6 alkoxycarbonyl Cl to C6 alkoxy, Cl to C6 alkoxycarbonyl Cl to C6 alkyl, cyano, hydroxy, mercapto, oxo and thioxo.), and represents oxygen, sulfur, imino or alkylimino 1 to 3 carbon atoms, R1 represents alkyl of 1 to 3 carbon atoms or haloalkyl of 1 to 3 carbon atoms, R2 represents alkyl of 1 to 3 carbon atoms, R3 represents, carboxy Cl to C6 alkyl, Cl to C6 alkoxycarbonyl Cl a C6 alkyl, Cl a C6 has 1 or 1 coxi ca rboni 1 Cl a C6 alkyl, C3 a C6 a 1 quen i lo xi carbon i 1 Cl a C6 alkyl, C3 to C6 has 1 or 1 quen i 1 ox i ca rbon i 1 Cl a C6 alkyl, C3 a C6 a 1 qu ini 1 ox i ca rbon i 1 Cl a C6 alkyl, C3 to C6 haloalkynyloxycarbonyl Cl to C 6 'alkyl, OR7, SR8 or N (R9) R10, X1 represents' halogen, cyano, thiocarbamoyl or nitro. X2 represents hydrogen or halogen. (wherein, each of R7, R8 and R10 independently represent carboxy Cl to C6 alkyl, Cl to C17 alkoxycarbonyl Cl to C6 alkyl, Cl to C6 has 1 or 1 cox i ca rbon i 1 Cl a C6 alkyl, C3 a C6 alkenyloxycarbonyl Cl to C6 alkyl, C3 to C6 haloalkeni loxycarbonyl Cl to C6 alkyl, C3 to C6 to 1 quiñi loxicarboni 1 Cl to C6 alkyl, C3 to C6 haloalkynyloxycarbonyl Cl to C6 alkyl, C3 to C8 cycloalkoxycarbonyl Cl to C6 alkyl, C3 to C8 hal or ci cl or 1 coxi ca rbo.?i 1 Cl a Cß alkyl, C3 to C8 ci cl or 1 queni 1 oxi ca rboni 1 Cl a C6 alkyl, C3 a C8 halocycloalqueni 1 oxycarboni 1 Cl a C6 alkyl, Cl a C6 alkoxycarbonyl Cl to C6 alkoxycarbonyl Cl to Cß alkyl, Cl to C8 to 1 qui 1 i denami nox i ca rbon i 1 Cl a Cß alkyl, f enox i ca rboni 1 Cl a C6 alkyl which can be substituted, phenyl Cl a C4 alkoxycarbonyl Cl to C6 alkyl which can be substituted, Cl to C6 to 1 coxi aminoca rboni 1 Cl to C6 alkyl, (Cl to C6 alkoxy) (Cl to C3 alkyl) aminocarbonyl Cl to C6 alkyl, Cl to C6 to 1 qu i 1 amino ca rboni 1 Cl a C6 alkyl, (Cl a C6 alkyl) Cl a C6 a 1 qu i 1 ami nocarbon i 1 Cl a C6 alkyl, phen i 1 ami noca rboni 1 Cl a C6 alkyl which can be substituted or phenyl Cl to C4 to which 1 aminocarboni 1 Cl to Cß alkyl which can be substituted, and R9 represents hydrogen or alkyl of 1 to 6 carbon atoms. ). ], and herbicides containing each of them as an effective ingredient.
In the present invention, as the group represented by Q-R3, for example, there are listed groups of the following formulas: [wherein, R is the same as defined above, each of Z1 and Z2 i ndependi in t men t represent hydrogen, halogen, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, haloalkenyl of 2 to 6 carbon atoms, alkynyl of 2 to 6 carbon atoms, halo to 1 quiñi 1 or of 2 to 6 carbon atoms, Cl to C6 alkoxy Cl to C6 alkyl, alkoxy of 1 to 6 carbon atoms, haloalkoxy of 1 to 6 carbon atoms, alkoxycarbonyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms or cyano (wherein, the halogen represented by Z1 or Z2 means fluorine, chlorine, bromine or iodine, and examples of the alkyl of 1 to 6 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl and the like, examples of the haloalkyl of 1 to 6 carbon atoms include bromomethyl, chloromethyl , fluoromethyl, dichloromethyl, trichloromethyl, difluoromethyl, chlorodi fluoromethoyl, bromodifluoro ethyl, trif luoromethyl, pentafluoroethyl, 2-f luoroethyl, 1,1-difluoroethyl, 2, 2, 2-tri cl or oe ti 1 o, 3,3,3-trif luor opropi lo, 3, 3, 3 - 1 ric 1 or Examples of the alkenyl of 2 to 6 carbon atoms include allyl, 1-methylthiol, 1,1-dimethylethyl, 2-methyl-1 to 1-yl, 1-butenyl, -butenyl, 3-butenyl and the like, examples of the haloalkenyl having from 2 to 6 carbon atoms include 1-chloro or 1 i 1 o, 1 -br omoa 1 i 1 o, 2-chloroallyl, 2, 3 -di cl or or alike, examples of the alkynyl of 2 to 6 carbon atoms include 2-propynyl, 1-methyl-2-propynyl, 1,1-dimethy1-2-prop opini 1, 2-butynyl, 3-butynyl, 1-methyl-2-butyl, and the like, examples of the haloalumyl which has 2 to 6 carbon atoms include 3-bromo-2-propyl or 1, 3-iodo-2. -propynyl, 1-f luoro-2-propyne, l-chloro-2-propynyl, 1-bromo-2-pr opini lo, l-chloro-2-butynyl and the like, examples of Cl to C6 alkoxy Cl to Cß alq Uilo include methoxymethyl, 2-methoxyethyl, 1-methoxyethyl, 3-methyl-oxypropyl 1, ethoxymethyl, 2-ethoxy-1, 3-ethoxypropyl 1, isopropoxymethyl, 2-i sopropoxyme and similar examples of alkoxy of 1 to β carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butyloxy, s-butyloxy, t-butyloxy and the like, examples of the haloalkoxy of 1 to 6 carbon atoms include chloromethoxy, bromomethoxy, dichloromethoxy , trichloromethyl ioxy, thiolororne ti 1 oxy, 2-f 1 or ti 1 oxy, 2,2,2-t-chloroethyloxy and the like, examples of Cl to C6 alkoxycarbonyl Cl to C6 alkoxy include methoxycarbonylmethoxy, ethoxycarbonylmethoxy, propoxy carboni lme toxi, is opropoxica rboni lme t oxy, 1 -me t oxycarbonile t oxy, 1 -et oxi ca rboni 1 et oxy, 1-propoxycarbonyletoxy, 1-isopropoxycarbonyletoxy, 2 -me toxy carboni let oxy, 2 -et ox carbon and 1-oxo, 2-propoxycarbonylethoxy, 2-isopropoxycarbonylethoxy and the like, examples of Cl to C6 alkoxycarbonyl Cl a C6 alkyl include methoxycarbonylmethoxy, ethoxycarbonylmethyl, propoxycarbonylmetho, isopropoxycarbonylmethyl, t-butoxycarbonylmethoxy, amyloxycarbonylmethyl, 1 -methioxycarbonyl 1, 1-ethoxycarbonyl and 1 or, 1-propoxycarbonylethyl, 1-isopropoxycarbonylethyl, 1 -butoxycarbonyl, 1-t-but oxycarbonyl and the like.). ] Examples of the carboxy Cl to C 6 alkyl represented by R 3 include carboxymethyl, 1-carboxyethyl, 2-carboxymethyl, and the like, examples of Cl to C 6 alkoxycarbonyl Cl to C 6 alkyl include me t oxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, is oppopox i ca rbon i Ime ti 1, bu toxi ca rbon i lme ti lo, isobutoxycarbonylmethyl, t-butoxycarbonylmethyl, amyloxycarbonylmethyl isoamyloxycarbonylmethyl, t-amyloxycarbonylmethyl, 1-methoxycarbonylethyl, 1-oxy oxycarbon I 1, -pr opoxica rboni 1 eti 1 o, 1-isopropoxy carboni lti lo, 1 -bu t oxi ca rbon i 1 eti 1 o, 1-isobut oxycarbonylethyl, 1-t-butoxycarbonylethyl, 2-methoxycarbonyl 1 eti 1, 2-ethoxycarbonylethyl and the like, examples of Cl to C6 haloalkoxycarbonyl Cl to C6 alkyl include chloromethyloxycarbonylimethyl, 2-fluoroethyloxycarbonymotimethyl, 2-chloropropyloxycarbonylmethoxy, 1-chloro-2-propyloxycarbonylmethyl, 2,2,2-trifluoroethyl loxicarboni lme tilo ysee jantes, examples of C3 a Cß alqueni loxicarboni 1 Cl a Cß alkyl include 1 i 1 ox i ca rboni lme ti ti o, 1-methyl-2-propenyloxycarbonylmethyl, 2-methyl-2-propeny loxycarboni lme ti it, 2-butenyloxycarbonylmethyl, 1-allyloxycarbonylethyl, 1- (1-methyl-2-propenyloxycarbonyl) ethyl, 1- (2-methyl-2-propenyloxycarbonyl) ethyl, 2-ali loxycarbonyl, 2- (2-methyl- 2-propeni 1 ox i ca rboni 1) eti 1 oy similar, examples of C3 to C6 has 1 or 1 that i1 oxi ca rbon i 1 Cl a C6 alkyl include 1 - cl or 1 i 1 i x i i i ti 1 o, l- (1-chloroalyloxycarbonyl) ethyl, 2-chloroalyloxycarbonylmethyl, 1 - (2-chloro or 1) oxy oxycarbon, and the like, examples of C3 to C6 to 1 qu ini 1 ox i ca rbon i 1 Cl to C6 alkyl include 1-methyl, 2-propyloxycarbonylmethyl, 1-methyl-2-propylene and 1-methyl-1-methyl-2-propylene. 1) eti 1, 2-propargyloxycarbonylethyl, 2- (1-methyl-2-propyne loxy carboni 1) ethylene and the like, examples of C3 to C6 haloalkynyloxycarbonyl Cl to C6 alkyl include • (3-chloro-2-propynyloxycarbonylmethyl) , l- (3-Chloro-2-propyne loxy carboni 1) et i lo, (1-chloro-2-propynyloxycarbonylmethyl, 1- (1-chloro-2-propyne loxycarboni 1) et al, and the like, examples of the alkylimino from 1 to 3 carbon atoms represented by Y include methylimino, ethylimino and the like, the alkyl of 1 to 3 carbon atoms represented by R 1 signifies methyl, ethyl, propyl, isopropyl, and examples of the haloalkyl of 1 to 3 carbons These include bromomethyl, chloromethyl, fluoromethyl, dichloromethyl, chlorodifluoromethyl, trichloromethyl, difluoromethyl, trifluoromethyl, pentafluoroethyl, 1,1-di-fluorite, 2,2,2-trifluoroetyl, 3, 3, 3 - fluorine opropyl 1 and the like, the alkyl of 1 to 3 carbon atoms represented by R 2 means methyl, ethyl, propyl or isopropyl, examples of the carboxy Cl to C 6 alkyl represented by R 'R include carboxymethyl, 1-carboxy The 2-carboxy et al and the like, examples of Cl to C6 alkoxycarbonyl Cl to C6 alkyl include oxocarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, oppopoxy carbonimethyl ether, butoxy carboni lme ti lo, isobutoxycarbonylmethyl, s-butoxycarbonylmethyl, t-b utoxycarbonylmethyl, amyloxycarbonylmethyl isotope, 1-oxycarbonyl, 1-t-amyloxycarbonylmethyl, 1 -methylcarbonyl-1 -eti 1, 1- ethoxycarbonylethyl, 1 -propoxy carboni le ti 1 o, 1-isopropoxycarbonileti 1-butoxycarbonylethyl, 1-is obut oxi ca rbon i 1 eti 1 o, 1-s-bu t oxi ca rbon i 1 eti 1 o, 1 - 1 -bu t oxi carboni le ti o, 2-me toxi carboni le ti lo, 2-oxycarboni let i lo, and the like, examples of Cl to C6 haloalkoxycarbonyl Cl to C6 alkyl include cyclohexylloxycarbonylimethyl, 2-fluoroe ti loxycarbonylimethyl, 2- chloropropyloxycarbonylmethyl, l-chloro-2-propyl-1-oxycarbonyl, 2,2,2-trifluoro-ti-loxycarbonylmethyl, and the like, examples of the C3-C-C-alkenyloxycarbonyl Cl to C-alkyl include 1 to 1 oxi ca rboni lme ti 1 or, 1-methyl-2-propeni loxi carboni lmet ilo, 2-methyl-2-pr openyloxycarbonylmethyl, 2-butenyloxycarbonylmethyl or 1-allyloxycarbonylethyl, 1- (l-methyl-2-propenyloxycarbonyl) ethyl, 1- (2-methyl-2-propenyloxycarbonyl) ethyl, 2-alkoxycarbon and 1-ethyl-1, 2- (l-methyl-2-propenyloxycarbonyl) ethyl, 2- (2-methyl-2- propeni 1 oxi coal i 1) eti 1 oy similar, examples of C3 to C6 ha 1 or lquen i 1 oxycarbon and 1 Cl to C6 alkyl include l-chloro-2-propenyloxy carbonylmethyl, 1 - (2-chloro-2-pr openi loxi coal i 1) eti lo and the like, examples of C3 to C6 to which i loxi ca rbon i 1 Cl. A C6 alkyl include pr ope rgi 1 ox i ca rbon i lme ti 1 o, l-metil-2-prop ini 1 ox i ca rbon i lme ti 1 o, 1-propargiloxicarboniletilo, 1 - (1 -me ti 1 -2 -prop i ni 1 ox i ca rbon i 1) eti 1, 2-propargyloxycarbonylethyl, 2- (1-methyl-2-propyne loxy carboni 1) et al and the like, examples of C3 to C6 haloalkynyloxycarbonyl Cl to C6 alkyl include 1 -br omo-2-pr opini lox i ca rbon i 1 methyl, 1- (1-chloro-2-propium loxycarbonyl) ethyl and the like, examples of C3 to C8 cycloalkoxy carboni 1 Cl to C6 alkyl include cyclopropyloxycarbonylmethyl, cyclohexyl thiol oxycarbonyl ether , 1- (1) and 1 (1) oxycarbon and the like, examples of C3 to C8 to 1 or to 1 coxycarbon C1 to C6 alkyl include 2,2-difluorocyclopentyloxycarbonylmethyl, 2- br omoci cl open ti loxi ca rboni lme ti 1 o, l- (2-chlorocicl obut i 1 ix i ca rbon i 1) et i 1y and similar examples of C3 to C8 ci cl oa 1 1 1 i i i i i C a C6 alkyl include 2-cyclopentenyloxycarbonylmethyl, 1 - (2-cyclobutyl) loxi carboni 1) et i lo and the like, examples of C3 to C8 ha 1 oci cl or lqueni 1 ox i carboni 1 Cl a C6 alkyl include 4-bromo-2-cyclobutenyloxycarbonylmethyl and 1 - (4 -b romo -2 -ci cl open t eni loxi ca rbon i 1) eti 1 oy similar, examples of Cl a C6 alkoxycarbonyl Cl a C6 alkoxycarbonyl Cl to C6 alkyl include methoxycarbonylmethoxycarbonylmethyl, 2- (methoxycarbonyl) -2-propoxycarbonylmethyl, 1- [1- (ethoxycarbonyl) and oxycarbonyl], and the like, examples of Cl to C8 To 1 qu i 1 idenami nox i ca rbon i 1 Cl a C6 alkyl include is opropi lidenaminoxica rboni lmet i lo, 2- (isopropilidenaminoxycarbonyl) ethyl and the like, examples of phenoxy ca rboni 1 Cl a C6 alkyl which can be substituted include phenoxycarbonyl, 1-phenoxycarbonylethyl, and the like, examples of the phenyl Cl to C4 alkoxycarbonyl Cl to C6 alkyl which can be substituted include benzyl 1-oxylcarbonylmethyl, 1-benzyloxycarbonyl 1 et al. and similar examples of Cl a C6 a 1 coxyamylcabon i 1 Cl a C6alkyl include oxoamide, rbonylmethyl, 1-methoxyaminocarbonylethyl, and oxyaminocarbonylmethyl, or 1-ethoxycarbonyl. et i 1 and similar examples of (Cl a C6 alkoxy) (Cl a C3 a 1 qu i 1) aminoca rbon i 1 Cl a C6 alkyl include (methoxy) (methyl) aminocarbonylmethyl, 1- (methoxy) (methyl) aminocarbonylethyl, (ethoxy) (me ti 1) aminocarbonylmethyl, 1- (ethoxy) (me ti 1) ami no Examples of Cl to C6 to 1 qui 1 aminocarbon i 1 Cl to C6 alkyl include 1-aminocarbonylmethyl, ethyl-aminocarbonylmethyl, isopropyl laminoca rbonylmethyl, 1-methylaminocarbonyltinyl, 1-isobutyl-aminocarbonyl and the like, examples of (Cl to C6 alkyl) (Cl to C6 alkyl) aminoca rboni 1 Cl to C6 alkyl include dimethylaminocarbonylmethyl, 1-dimethylaminocarbonyl ethyl and the like, examples of the Laminoca rboni 1 Cl a C6 alkyl which can be substituted include phenylamino carbon i lme ti 1 o, 1-phenylaminocarboni tile and the like, and examples of phenyl Cl a C4 to 1 qui 1 aminocarboni 1 Cl a Cß alkyl which it can be substituted, include benzaminocarbonylmethyl, 1-benzyl, aminocarbonyl, and the like, examples of the alkyl of 1 to 6 carbon atoms represented by R 9 include methyl, ethyl, propyl, isopropyl, butyl and the like, and the halogen represented by X 1 and X 2 mean fluorine, chlorine, bromine or iodine. In the present compounds, from the starting point of the herbicidal activity, those are preferable where Q-R3 is Q1, Q-2 or Q-6, Y is oxygen or sulfur, more preferably oxygen, R1 is methyl substituted with fluorine (for example, trifluoromethyl, chlorodifluorometyl, difluoromethyl or the like), or ethyl substituted with fluorine (for example, pen taf luor oe ti 1 or, 1,1- di f luoroe ti lo or the like), in more preferably trifluoromethyl, R2 e's ethyl or ethyl, more preferably methyl, R3 is Cl to C4 alkoxycarbonyl Cl to C4 alkyl, Cl to C4 alkoxycarbonyl Cl to C4 alkoxy, C3 to C7 to 1 cox i carbon i 1 Cl to C4 alkoxy, Cl to C4 alkoxycarbonyl Cl to C4 alkylthio or Cl to C4 alkoxycarbonyl Cl to C4 alkylamino, most preferably Cl to C2 alkoxycarbonyl Cl to C2 alkoxy, X1 is halogen, most preferably chlorine, and / or X2 is halogen, more preferably fluorine. Sometimes, geometric isomers based on double bond, optical isomers and diastereomers based on asymmetric carbon, may be present in the present compound, and the present compound also includes these isomers and mixtures thereof. Next, methods for the production of the present compounds will be illustrated.
The present compound can be produced, for example, by the following (Production Method 1) to (Production Methods 10). (Production Method 1) Of the present compounds, the compound [I] wherein R3 is OR7, SR8 or N (R9) R10 can be produced by reacting a compound [III] of the formula [III] [wherein, R1, R2, Y, Q, X1 and X2 are the same as defined above, and W represents oxygen, sulfur, imino or, alkylimino of 1 to 3 carbon atoms such as methylimino and the like . ] with a compound [IV] of the formula [IV] R 11 -R 12 [IV] [wherein, R 11 represents carboxy Cl to C 6 alkyl, Cl to C 6 alkoxycarbonyl Cl to C 6 alkyl, Cl to C 1 haloalkoxycarbonyl Cl to C 3 alkyl, C 3 to C 6 lican 1 oxy rbon i 1 Cl C6 alkyl, C3 to Cß alkynyloxycarbonyl Cl to C6 alkyl, phenoxycarbonyl Cl to C6 alkyl which can be substituted, phenyl Cl to C4 alkoxycarbonyl Cl to Cß alkyl which can be substituted, Cl to Cβ to coxyaminocarboni 1 Cl to Cß alkyl, ( Cl a C 2 alkoxy) (Cl a C 3 to l 1) ami no carboni 1 Cl a C6 alkyl, Cl a C a 1 a 1 a 1 ami noca rbon i 1 Cl a C6 alkyl, (Cl a C6 alky) Cl a C6 a 1 qui 1 ami no ca rboni 1 Cl a C6 alkyl, phenyl 1 aminoca rboni 1 Cl a C6 alkyl that can be substituted, or phenyl Cl a C4 alkylaminocarboni 1 Cl a C6 alkyl which can be substituted, and R12 represents a separation group such as chlorine, bromine, iodine, me t ans ul f oni 1 ox i, pt o luens u 1 fon i 1 ox i and similar. ] in the presence of a base. This reaction is usually conducted in a solvent, and the reaction temperature is usually in a range of 0 to 200 ° C, and the reaction time is usually in a range from the instant to 72 hours.
With respect to the amounts of reactants that are reacted, it is theoretically that the amount of the compound [? V] is 1 mole and the amount of the base is 1 mole based on 1 mole of the compound [III], however, the ratio It can be changed in an optional way depending on the reaction conditions. As the base used, there are listed organic bases such as pyridine, quinoline, benzylimethyl, 1-amine, N-methylmorpholine, 1, 8-diazabicyclo [5.4.0] undec-7-enc, 1,5-diazabicyclo [4.3.0 ] non-5-ene, 1,4-di a zabi ciclo [2.2.2] oct ano, 4-dimethylaminopyridine, N, N -dime ti 1 ani 1 ina, N, N-di eti 1 ani 1 ina, triethylamine , tri-n-propylamine, triisopropylamine, tri-n-butylamine, diisopropylethylamine and the like, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium hydrogen carbonate , potassium hydrogen carbonate, sodium hydride, potassium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like.
As the solvent used, there are listed, for example, aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether and the like, aromatic hydrocarbons such as benzene, toluene, xylene and the like, aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, ben zot rif luoride and the like, ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, dioxane, tetrahydrofuran, dimethyl ether of ethylene glycol, diglyme and the like, ketones such as acetone, 2-butanone , methyl isobutyl ketone and the like, esters such as ethyl formate, ethyl acetate, butyl acetate, diethyl carbonate and the like, nitro compounds such as nitromethane, nitrobenzene and the like, nitriles such as acetonitrile, is obu tir oni tri 1 oy similar, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyridone and the like, sulfur compounds such as sulfoxide of dimethyl, sulfolane and the like, or mixtures thereof. After completion of the reaction, a present compound intended can be obtained, for example, by the following operation 1) or 2). 1) The reaction solution is poured into water, this is extracted with an organic solvent, and the organic layer is dried and concentrated. 2) The reaction solution is concentrated as is, or, filtered if necessary, and the filtrate is concentrated. The resulting present compound can also be purified by an operation such as chromatography, re c r i s t a 1 i z a tion and the like.
(Production Method 2) Of the present compounds, the compound [I] wherein R3 is OR7 can be produced by reacting a compound [V] of the formula [V] [wherein, R1, R2, Y, Q, X1 and X2 are the same as defined above.] with an alcohol compound [VI] of the formula [VI] R'-OH [VI] [where, R7 is the same as it was defined before. ] in the presence of a dehydrated reagent. This reaction is usually conducted in a solvent, and the reaction temperature is usually in a range of -20 to 150 ° C, preferably from 0 to 100 ° C, and the reaction time is usually in a range from the first instant. at 48 hours. As the dehydration reagent, for example, combinations of triarylphosphine such as triphenylphosphine and the like, and di (alkyl in ferrum) to zodicarboxylate such as diethyl azodicarboxylate, diisopropyl azodicarboxylate and the like are listed. With respect to the amounts of reagents that are reacted, the amount of the alcohol compound [VI] is from 1 to 3 mol, preferably from 1 to 1.5 mol, the amount of the triarylphosphine used as a dehydrating agent is from 1 to 3 mol, pref erably from 1 to 1.5 mol, and the amount of a di (alkyl in f er io r) az odi ca rboxi 1 ato is from 1 to 3 mol, preferably from 1 to 1.5 mol , based on 1 mol of the compound [V]. The proportion of these reagents can optionally be changed depending on the reaction conditions. As the solvent used, there are listed, for example, aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether and the like, aromatic hydrocarbons such as toluene, xylene and the like, aromatic halogenated hydrocarbons such as chlorobenzene. , ben zotrif 1 uo ruroy alike, ethers such as diethyl ether, diisopropyl ether, dioxane, THF, dimethyl ether of ti 1 eng 1 i co 1, and the like, esters such as ethyl acetate and the like, or mixtures thereof. After completion of the reaction, a present compound intended can be obtained, for example, by the following operation 1) or 2). 1) The reaction solution is poured into water, this is extracted with an organic solvent, and the organic layer is dried and concentrated, and the residue is subjected to joke photography. 2) The reaction solution is concentrated as it is, and the residue is subjected to chromatography. The resultant present compound was also purified by an operation such as r e cr i s t a l i ation and the like, in some cases.
(Production Method 3) Of the present compounds, some compounds can be produced using a carboxylic acid compound [VIII] of the formula [VII] [wherein, R1, R2, Y, Q, X1, X2 and W are the same as defined antirement, R13 represents alkylidene of 1 to 6 carbon atoms or alkylene of 2 to 6 carbon atoms and m represents a number integer of 0 or 1.] and an alcohol compound [VIII] of the formula [VIII] HO-R14 [VIII] [wherein, R14 represents alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, alkenyl of 3 to 6 carbon atoms, haloalkenyl of 3 to 6 carbon atoms, alkynyl of 3 to 6 carbon atoms carbon or has 1 or 1 qu ini of 3 to 6 carbon atoms.] as raw materials. This reaction is conducted, for example, by reacting the carboxylic acid compound [VII] with a chlorinating agent t to give an acid chloride (preferably described above, referred to as < Process \ 3 - 1 >) , then, reacting the acid chloride with the alcohol compound [VIII] in the presence of a base (described below, referred to as < Process 3 -2 >). The < Process 3-l > it is conducted without a solvent or in a solvent, and the reaction temperature is usually in a range from 0 to 150 ° C and the reaction time is usually in a range from the first instant to 24 hours. With respect to the amounts of reactants that are reacted, it is theoretically that the amount of the chlorinating agent is 1 mol based on 1 mol of the carboxylic acid compound [VII], however, the proportion can be optionally changed depending on the reaction conditions. As the chlorinating agent used, for example, thionyl chloride, sulfuryl chloride, phosgene, oxalyl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and the like are listed. As the solvent used, there are listed, for example, aliphatic hydrocarbons such as n-hexane, n-heptane, nonane, decane, ligroin, cyclohexane, petroleum ether and the like, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene and the like , aliphatic halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dihydrogen chloride, 1,2,3-tri chloro pulopane and the like, aliphatic halogenated hydrocarbons such as monochlorobenzene, dichlorobenzene , benz'o trif 1 uo rur and similar, ethers such as diethyl ether, diisopropyl ether, methyl ether 1 - 1 -bu ti 1 i co, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme and the like esters such as ethyl acetate and the like, or mixtures of the same, After the completion of the reaction, for example, the reaction solution is concentrated, and the concentrated residue is used as it is in the <; Process 3-2 > . The < Process 3-2 > it is conducted without a solvent or in a solvent, and the reaction temperature is usually in a range from -20 to 100 ° C and the reaction time is usually in a range from the first moment to 24 hours. With respect to the amounts of reagents that are reacted, it is theoretically intended that the amounts of the alcohol compound [VIII] and the base are 1 mole, respectively, based on 1 mole of the carboxylic acid compound [VII] used in the <; Process 3-l > , however, the ratio or proportion may optionally be changed depending on the reaction conditions. As the base used, there are listed, for example, inorganic bases such as sodium hydrogen carbonate, potassium hydrogen carbonate, lithium carbonate, sodium carbonate, potassium carbonate and the like, nitrogen-containing aromatic compounds such as pyridine, quinoline, 4 -dime ti 1 aminopi r idi na, 2-picoline, 3-picoline, 4-picoline, 2, 3 - 1 uti di na, 2, 4 - 1 ut idi na, 2, 5 - 1 uti di na, 2 , 6 - lut i dina, 3,4-lutidine, 3, 5 - 1 ut idina, 3 -chloropi r idine, 2-ethyl-3 -eti lp i di ri na, 5 -eti 1 -2 -me ti lp i di kidney and the like, and tertiary amines such as triethylamine, diisopropylethylamine, tri-n-propylamine, tri-n-bu tylamine, benzyl-1-diene-1-amino, N-methylmorpholine, 1,8-diazabicyclo [ 5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene, 1,4-dia z abici [2.2.2] oc ean and the like. As the solvent used, there are listed, for example, aliphatic hydrocarbons such as n-hexane, n-heptane, nonane, decane, ligroin, cyclohexane, petroleum ether and the like, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene and the like. similar, aliphatic halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,2,3,1-chloropropane and the like, aromatic halogenated hydrocarbons such as monochlorobenzene, dichlorobenzene, ben zot and fluoride and the like, ethers such as diethyl ether, diisopropyl ether, methyl ether 1-t-bu ti 1 i co, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme and the like, esters such as ethyl acetate and the like, or mixtures thereof. After completion of the reaction, a present compound intended can be obtained, for example, by the following operation 1) or 2). 1) The reaction solution is poured into water, this is extracted with an organic solvent, and the organic layer is dried and concentrated. 2) The reaction solution is concentrated as it is, or, filtered if necessary, and the filtrate is concentrated. The resulting present compound can also be purified by an operation such as chromatography, recrystallization and the like. This reaction can also be conducted by reacting the compound [VII] with the compound [VIII] in the presence of a condensation agent with a base or without a base in a solvent. The reaction temperature is usually in a range from 0 to 100 ° C, and the reaction time is usually in a range from the first time to 48 hours. As the condensing reagent, carbonyldiimidazole, di-cyclohexyl-1-carbamate, di- [3- (dimethylamino) propyl] -3-ethylcarbodiimide hydrochloride and the like are listed. As the base, organic bases such as triethylamine, diisopropylethylamine and the like are listed. With respect to the amounts of reactants that are reacted, the amount of the compound [VIII] is from 1 to 3 mol, the amount of the condensation reagent is from 1 to 3 mol, the amount of the base is from 0.5 to 3 mol , based on 1 mol of the compound [VII]. The ratio or proportion of these reagents can be optionally changed depending on the reaction conditions. As the solvent used, chloroform, amide such as N, N-dimethylformamide, ethers such as tetrahydrofuran, and the like, or mixtures of the same, are listed. After the completion of the reaction, a desired present compound can be obtained, for example, by the reaction solution being poured into water, this is extracted with an organic solvent, and the organic layer is dried and concentrated. The resulting present compound can also be purified by an operation such as chromatography, recrystallization and the like. In addition, this reaction can also be conducted by a method in which a reaction is conducted in the presence of an acid catalyst, other known methods, in addition to the methods mentioned above.
(Production Method 4) Of the present compounds, the compound [I] wherein X1 is cyano can be produced by reacting a uracil compound [IX] of the formula [IX] [where R- and X- are the same as defined by an e r i ormen, and R 15 represents fluorine, chlorine, bromine or iodine.] with a compound [X] of the formula [X] [where, Y, Q and R3 are the same as defined above.] in the presence of a base.
This reaction is commonly conducted without a solvent or in a solvent, and the reaction temperature is usually in a range from 0 to 200 ° C, and the reaction time is usually in a range from the first time to 24 hours. With respect to the quantities of reactants that are reacted, it is theoretical that the amount of compound [X] is 1 mole and the amount of the base is 1 mole based on 1 mole of the compound uracil [IX], however, the ratio or proportion can be changed optionally depending on the reaction conditions. As the base used, organic bases are listed such as 1,8-diazabicyclo [5.4.0] undec-7-ene, 4-dimime ti 1 ami nop iri di na, N, N -d ime ti 1 ani 1 i na , N, N-diethylamine, triethylamine, diisopropylethylamine and the like, and organic bases such as lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, carbonate. barium, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like. As the solvent used, there are listed, for example, aliphatic hydrocarbons such as n-hexane, n-heptane, and the like, aromatic hydrocarbons such as toluene, xylene and the like, aromatic halogenated hydrocarbons such as chlorobenzene, ben zotrif 1 oryor similar, ethers such as diethyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme and the like, ketones such as methyl isobutyl ketone and the like, esters such as ethyl acetate, butyl acetate and the like, nitriles such as acetonitrile, is obut Examples of such compounds are amides such as N, N-dimethylammonium, N-methyl-2-pyrrolidone and the like, sulfur compounds such as dimethisulfoxide, sulfolane and the like, or mixtures thereof.
This reaction can sometimes be accelerated by using a catalyst. As the catalyst, copper iodide, copper bromide, copper chloride, copper powder and the like are listed, and the amount of the catalyst to be used in the reaction is from 0.0001 to 1 mole based on 1 mole of the uracil compound [IX ], and this ratio or proportion can optionally be changed depending on the reaction conditions.
After the. termination of the reaction, an intended present compound can be obtained, for example, by the following operation 1) or 2). 1) The reaction solution is poured into water, this is extracted with an organic solvent, and the organic layer is dried and concentrated. 2) The reaction solution is concentrated as is, or, filtered if necessary, and the filtrate is concentrated. The resultant present compound was also purified by an operation such as chromatography, reaction and the like.
(Production Method 5 The present compound can be produced by reacting a uracil compound [XI] of the formula [XI] [wherein, R1, R2, Y, X1 and X2 are the same as defined above.] with a compound [XII] of the formula [XII] [wherein, R16 represents a separation group such as fluorine, chlorine, bromine, iodine, its 1 f on i 1 oxy, its 1 f on and 1 and similar, and R 3 is equal as defined above. ] in the presence of a base. This reaction is usually conducted without a solvent or in a solvent, and the reaction temperature is usually in a range from room temperature to 200 ° C, and the reaction time is usually in a range from the first instant to 24 hours. With respect to the amounts of reactants that are reacted, it is theoretically the amount of compound [XII] to be 1 mole and the amount of the / base to be 1 mole based on 1 mole of compound [XI], however, the proportion or amount can optionally be changed depending on the reaction conditions. As the base used, organic bases such as N-methylmorpholine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 4-dimethylaminopyridine, N, N -dime ti 1 an i 1 ina, N, N are listed. -di eti lani 1 ina, triethylamine, diisopropylethylamine and the like, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, hydride sodium, potassium hydride, sodium hydroxide, potassium hydroxide, and so on. As the solvent used, there are listed, for example, aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether and the like, aromatic hydrocarbons such as toluene, xylene and the like, aromatic halogenated hydrocarbons such as c 1 orobenzene, ben zotrif luo rur and the like, ethers such as diethyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme and the like, ketones such as acetone, 2-butanone, methyl isobutyl ketone and the like, esters such as ethyl acetate, butyl acetate, and the like, nitriles such as acetonitrile, isobundant and similar, amides such as N, -methylethylformamide, N, N-dimethylethyl amide, N-me ti 1 -2 pyrrolidone and the like, sulfur compounds such as dimethisulfoxide, sulfolane and the like, or mixtures thereof. This reaction can sometimes be accelerated by using a catalyst. The amount of the catalyst to be used in the reaction is preferably from 0.0001 to 1 mol based on 1 mol of the compound [IX], and this ratio or proportion can be optionally changed depending on the reaction conditions.
As the catalyst, copper compounds such as copper iodide, copper bromide, copper chloride, copper powder, and the like, and copper ethers are listed. crown such as 12-crown-4, 15-crown-5, 18-crown-6 and seme j before. After completion of the reaction, a present compound, intended, for example, by the following operation 1) 6 2) can be obtained. 1) The reaction solution is poured into water, this is extracted with an organic solvent, and the organic layer is dried and concentrated. 2) The reaction solution is concentrated as is, or, filtered if necessary, and the filtrate is concentrated. The intended compound can also be purified by an operation such as chromatography, recrystallization and the like.
(Production Method 6) The present compound can be produced by reacting a uracil compound [XXXI] of the formula [XXXI] [where, R1, R2, Y ', Q, X1 and X2 are the same as they were defined ant er iorment e. ] with a compound [XXXX] of the formula [XXXX] [where, R2 and R12 are the same as they were defined ant e ri or rmen t. ] in the presence of a base.
This reaction is usually conducted without a solvent or in a solvent, and the reaction temperature is usually in a range from -20 to 150 ° C, and the reaction time is usually in a range from the first moment to 24 hours.
With respect to the amounts of reactants that are reacted, it is theoretically desirable that the amount of compound [XXXX] be 1 mol and the amount of the base be 1 mol based on 1 mol of the compound uracil [XXXI], however, the proportion or amount can optionally be changed depending on the reaction conditions.
As the base used, organic bases are listed such as pyridine, quinoline, ben cimidimet i 1 amine, N-methylmorpholine, 1,8-di az abi ci cl or [5.4.0] undec-7-ene, 1, 5-diazabicyclo [4.3.0] non-5-ene, 1,4-di az abi ci cl or [2.2.2] oc ta no, 4-dimethylaminopyridine, N, N -d ime ti 1 ani 1 ina, N , N-di et i-lani-1-one, triethylamine, tri-n-pr or i-amine, tri-sopropylamine, tri-n-butylamine, diisopropylethylamine and the like, metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide and the like, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, hydride potassium, lithium hydroxide, sodium hydroxide, potassium hydroxide, and similar before. As the solvent used, there are listed, for example, aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether and the like, aromatic hydrocarbons such as benzene, toluene, xylene and the like, aromatic halogenated hydrocarbons such such as chlorobenzene, dichlorobenzene, benzotri fluoride and the like, ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, dioxane, tetrahydrofuran, dimethyl ether of 1-methyl-1-ene, diglyme and the like, ketones such as acetone, 2-butanone, methyl isobutyl ketone and the like, esters such as ethyl acetate, butyl acetate, and the like, nitro compounds such as nitromethane, nitrobenzene and the like, nitriles such as acetonitrile, isobundant onyl and the like, amides such as N, N-dime ti lf ormamide, N, N -dime ti 1 ace t ami da, N-me t il-2-pi rrolidone and the like, sulfur compounds such as dimethyl t 1 its oxide , sulfolane and the like, alcohols such as methanol, ethanol, ethylene glycol, isopropanol, t-butanol and the like, or mixtures thereof. After completion of the reaction, a present compound, intended, for example, by the following operation 1 '), 2) or 3) can be obtained. 1) The reaction solution is poured into water, this is extracted with an organic solvent, and the organic layer is dried and concentrated. 2) The reaction mixture is poured into water and the precipitate is collected by filtration. 3) A reaction solution is concentrated as is, or filtered if necessary, and the filtrate is concentrated. The resulting present compound can also be purified by an operation such as chromatography, recrystallization and the like.
(Production Method 7) Of the present compounds, the compound [I] wherein Q is a pyrazoldiyl group can be produced by a method shown in the following scheme. [wherein, R1, R2, R11, R12, X1 and X2 are the same as defined above. R20 represents lower alkyl such as methyl, ethyl and the like, R21 represents hydrogen, alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms or alkynyl of 2 to 6 carbon atoms, R22 represents alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms or alkynyl of 2 to 6 carbon atoms, and Y 1 represents oxygen, sulfur or alkyne. ] < Step A > : A process for producing the compound [XXXIII] from the compound [XXXII].
The compound [XXXIII] can be produced by reacting the compound [XXXII] with the compound [XXXXII] in the presence of a base. This reaction is usually conducted without a solvent or in a solvent, and the reaction temperature is usually in a range from 0 to 150 ° C, and the reaction time is usually in a range from the first time to 24 hours. With respect to the amounts of reactants that are reacted, it is expected that the amount of compound [XXXXII] is 1 mole and the amount of the base is 1 mole based on 1 mole of compound [XXXII], however, the The proportion or quantity can optionally be changed depending on the reaction conditions.
As the base used, organic bases are listed such as pyridine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 4-dimet and laminopi ridine,, N -dime ti 1 an i 1 i Na, N, N-diethylaniline, triethylamine, diisopropyl and tin, and the like, metal alkoxides such as sodium methoxide, potassium t-butoxide and the like, and inorganic bases such as lithium carbonate, -carbonate of sodium, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like. As the solvent used, there are listed, for example, aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, petroleum ether and the like, aromatic hydrocarbons such as toluene, xylene and the like, aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene. , ben zotrif 1 uo ruroy alike, ethers such as diethyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and the like, cotones such as acetone, 2-butanone, methyl isobutyl ketone and the like, esters such as ethyl acetate, and the like, nitriles such as acetonitrile, sobutylium and the like, amides such as N, -dimethyl-ilformamide, N-methyl-1-pyridone and the like, sulfur compounds such as dimethisulfoxide, sulfolane and the like, alcohols such such as methanol, ethanol, t-butanol and the like, or mixtures thereof. After completion of the reaction, a present compound, intended, for example, by the following operation 1) or 2) can be obtained. 1) The reaction solution is poured into water, extracted with an organic solvent, and the organic layer is dried and concentrated. 2) The reaction solution is concentrated as is, or, filtered if necessary, and the filtrate is concentrated. The desired compound can also be purified by an operation such as chromatography, recrystallization and the like. < Step b > : A process for producing compound [XXXIV] from compound [XXXIII].
The compound [XXXIV] can be produced by reacting the compound [XXXIII] with a formylating agent in the presence of a base. This reaction is usually conducted without a solvent or in a solvent, and the reaction temperature is usually in a range from 0 to 100 ° C, and the reaction time is usually in a range from the first moment to 24 hours. With respect to the amounts of reactants that are reacted, it is theoretically necessary that the amount of the formylation agent be 1 mole and the amount of the base is 1 mole based on 1 mole of the compound [XXXIII], however, the proportion or amount can optionally be changed depending on the reaction conditions. As the base used, metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide and the like are listed, and inorganic bases such as sodium hydride, potassium hydride, lithium hydroxide, sodium hydroxide, hydroxide potassium, and s eme j before. As the solvent used, there are listed, for example, ethers such as diethyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme and the like, ketones such as acetone., 2-butanone, methyl isobutyl ketone and the like, esters such as ethyl acetate, butyl acetate, and the like, or mixtures thereof. After completion of the reaction, a desired compound present can be obtained, for example, by the following operation 1) or 2). 1) The reaction solution is poured into water, this is extracted with an organic solvent, and the organic layer is dried and concentrated. 2) The reaction solution is concentrated as is, or, filtered if necessary, and the filtrate is concentrated. The desired compound can also be purified by an operation such as chromatography, recrystallization and the like. < Step c (R, 21 is not hydrogen) > : A process for producing compound [XXXIV] from compound [XXXII].
Compound [XXXIV] can be produced by reacting compound [XXXII] with compound [XXXXIII] in the presence of a base. This reaction is usually conducted without a solvent or in a solvent, and the reaction temperature is usually in a range from 0 to 150 ° C, and the reaction time is usually in a range from the first time to 24 hours. . With respect to the amounts of reactants that are reacted, it is theoretically the amount of compound [XXXXIII] to be 1 mol and the amount of the base to be 1 mol based on 1 mol of compound [XXXII], however, the proportion or quantity can be changed optionally depending on the reaction conditions. As the base used, organic bases are listed such as pyridine, quinoline, benzyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 4-dimethylaminopyridine, N, N-dime ti 1 anhydride, N, N-diethylane-1-ane, triethylamine, diisopropylethylamine and the like, metal alkoxides such as potassium t-butoxide and the like, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate , sodium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like. As the solvent used, there are listed, for example, aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, petroleum ether and the like, aromatic hydrocarbons such as toluene, xylene and the like, aromatic halogenated hydrocarbons such as chlorobenzene, benzot fluoride and the like, ethers such as dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and the like, ketones such as acetone, 2-butanone, methyl isobutyl ketone and the like, esters such as ethyl acetate, butyl acetate, and the like, nitriles such as acetonitrile, isomers and the like, amides such as N, N-dimethylformamide, N, N-dimethyl-1-acetylamide, N-methyl-pyrrolidone and the like, sulfur compounds such as dimethyl sulfoxide, sulfolane and the like, or mixtures thereof. After completion of the reaction, a present compound intended, for example, by the following operation 1) or 2) can be obtained. 1) The reaction solution is poured into water, this is extracted with an organic solvent, and the organic layer is dried and concentrated. 2) The reaction solution is concentrated as is, or, filtered if necessary, and the filtrate is concentrated. The desired compound can also be purified by an operation such as chromatography, re cr i s t a 1 i z ation and the like. < Step d > : A process for producing compound [XXXV] of compound [XXXIV].
The compound [XXXV] can be produced, for example, by reacting the compound [XXXIV] with a hydrazine compound in a solvent. The reaction temperature is in a range from 0 to 200 ° C, preferably from room temperature to reflux temperature. The reaction time is usually in a range from the first moment to 24 hour s.
With respect to the amounts of reactants that are reacted, it is theoretically that the amount of the hydrazine compound is 1 mole based on 1 mole of the compound [XXXIV], however, option or the amount or amount can be changed depending on of the reaction conditions. As the hydrazine compound used, hydrazine monohydrate, methyl carbazate and the like are listed. As the solvent used, there are listed, for example, aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, - petroleum ether and the like, aromatic hydrocarbons such as toluene, xylene and the like, aromatic halogenated hydrocarbons such as chlorobenzene, ben zot ri fluoride and the like, alcohol such as methanol, ethanol and the like. The reaction solution after completion of the reaction can be poured into water and the precipitated crystals are collected by filtration, or subjected to customary methods such as extraction with an organic solvent, neutralization, concentration and the like, to obtain a wanted compound.
The desired compound can also be purified by an operation such as chromatography, recrystallization and the like. < Step e > : A process for producing the compound [XXXVI] from the, 'compound [XXXV].
The compound [XXXVI] can be produced by reacting the compound [XXXV] A) with the compound [IV] in the presence of a base, 0 B) with the alcohol compound [VI] in the presence of a dehydrating agent. A) This reaction is usually conducted without a solvent or in a solvent, and the reaction temperature is in a range from 0 to 200 ° C, and the reaction time is usually in a range from the first moment to 24 hours. With respect to the amounts of reactants that are reacted, it is theoretically the amount of the compound [VI] to be 1 mol and the amount of the base to be 1 mol based on 1 mole of the compound [XXXV], however, optionally the proportion or amount can be changed depending on the reaction conditions. As the base used, organic bases such as pyridine, Idimeti lamin beni, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] a dec-7-ene, 4-dimethylaminopyridine, N, N-d ime ti 1 are listed. ani-1-one, N, N-di-et-ilane-1-ane, triethylamine, diisopropylethylamine and the like, metal alkoxides such as sodium methoxide, potassium t-butoxide and the like, and inorganic bases such as lithium carbonate, sodium carbonate, carbonate of potassium, lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like. As the solvent used, there are listed, for example, aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether and the like, aromatic hydrocarbons such as benzene, toluene, xylene and the like, aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, ben zotrif luor uro and the like, ethers such as diethyl ether, dioxane, tetrahydrofuran, dimethyl ether of 1-glycol 1, diglyme and the like, ketones such as acetone, 2-butanone, methyl isobutyl ketone and the like, esters such as ethyl acetate, butyl acetate, and the like, nitro compounds such as nitromethane, nitrobenzene and the like, nitriles such as acetonitrile, isobutyl ironi tri and the like, amides such as N, N-dimet and formamide, , N-dimethylacetylamide, N-me ti 1-2 -pyridone and the like, sulfur compounds such as dimethisulfoxide, sulfolane and the like, alcohols such as methanol, ethanol, ethanol ilenglicol, isopropanol, t-butanol and the like, or mixtures thereof. After completion of the reaction, a desired compound can be obtained, for example, by pouring the reaction solution into water, extracting it with an organic solvent, and drying and concentrating the organic layer. The desired compound can also be purified by an operation such as chromatography, r e cr i s t a l i z ation and the like.
B) The reaction is usually conducted in a solvent, and the reaction temperature is usually in a range from -20 to 150 ° C, preferably from 0 to 100 ° C, and the reaction time is usually in a range from the first moment up to 48 hours.
As the dehydrating reagent, for example, combinations of triarylphosphine such as triphenylphosphine and the like, and di (lower alkyl) to zodi caboxylate, such as diethyl azodicarboxylate, diisopropyl azodicarboxylate and the like are listed.
With respect to the amounts of the reactants to be reacted, the amount of the alcohol compound [VI] is from 1 to 3 mol, preferably from 1 to 1.5 mol, the amount of the triarylphosphine used as a dehydrating agent is from 1 to 3 mol, preferably from 1 to 1.5 mol, and the amount of di (lower alkyl) to zodi carboxy is from 1 to 3 mol, preferably from 1 to 1.5 mol, based on 1 mol of the compound [ XXXV]. The proportion of these reagents can optionally be changed depending on the reaction conditions. As the solvent usedAliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether and the like are listed, such as aromatic hydrocarbons such as benzene, toluene, xylene and the like, halogenated aromatic hydrocarbons such as chlorobenzene, ben zotrif 1 or ro roy, ethers such as diethyl ether, diisopropyl ether, dioxane, THF, ethylene glycol dimethyl ether, diglyme and the like, esters such as ethyl acetate, and the like, or mixtures thereof. After completion of the reaction, a desired compound can be obtained, for example, by subjecting the reaction solution to customary methods such as addition of water, and then extraction with an organic solvent, concentration and the like. The desired compound can also be purified by an operation such as chromatography, recrystallization and the like. < Step f > : A process for producing the compound [XXXVII] from the compound [XXXVI].
The compound [XXXVII] can be produced by reacting the compound [-XXXVI] with a compound [XXXXIV] of the formula [XXXXIV] R 2 -R12 [XXXXIV] [where, R12 and R22 are the same as defined above.] in the presence of a base. This reaction is usually conducted without a solvent or in a solvent, and the reaction temperature is in a range from 0 to 200 ° C, and the reaction time is usually in a range from the first moment to 24 hour s. With respect to the amounts of the reactants to be reacted, it is theoretically desirable that the amount of the compound [XXXXIV] be 1 mol, and the amount of the base be 1 mol based on 1 mol of the compound [XXXVI], however, the The proportion can optionally be changed depending on the reaction conditions.
As the base used, organic bases are listed such as pyridine, N-methylmorpholine, 1, 8-diazabicyclo [5.4.0] undec-7-ene, 4-dimethylaminopyridine,, N-dime ti 1 ani 1 i na, N, N-diet i lani lina, triethylamine, 'diisopropylethylamine,' and the like, metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide and the like, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, sodium hydride, hydride potassium, lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like. As the solvent used, there are listed, for example, aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether and the like, aromatic hydrocarbons such as toluene, xylene and the like, halogenated aromatic hydrocarbons such as chlorobenzene, ben zotri fluoride and the like, ethers such as diethyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme and the like, ketones such as acetone, 2-butanone, methyl isobutyl ketone and the like, esters such as ethyl acetate, and the like, nitriles such as acetonitrile, is obut ironitrile and the like, amides such as N, N-dimethy1-formamide, N-methyl-2-pyridinone and the like, sulfur compounds such as dimethisulfoxide, sulfolane and the like, alcohols such as methanol, ethanol, et i lengl i col. - 1-but anol and the like, or mixtures thereof. After the completion of the reaction, a desired compound can be obtained by pouring the reaction solution into water and collecting the precipitated crystals by filtration, or by pouring the reaction solution into water, then the mixture is subjected to after-treatment. Uses such as extraction with an organic solvent, concentration and s. The desired compound can also be purified by an operation such as chromatography, recrystallization and the like. (Production Method 8) The present compound can be produced shown in the following scheme. [wherein, R1, R2, R11, W, Y, Q, X1 and X2 are the same as or were defined one third, A ~ represents the opposite anion of the diazonium ion as Cl ", BF4", CF_S03 ~ and the like .]. < Step 8-l > : A process for producing the compound [XXXXVI] from the compound [XXIII]. The compound [XXXXVI] can be produced, for example, by reacting the compound [XXIII] with a diazotizing agent and an acid in a solvent. The reaction temperature is from -30 to 30 ° C, and the reaction time is usually from the first moment to 10 hours.
With respect to the amounts of reactants that are reacted, the amount of the diazotizing agent is from 1 mol to 3 mol, and the amount of the acid is from 1 mol to 6 mol based on 1 mol of the compound. [XXIII], however, the proportion or amount may optionally be changed depending on the reaction conditions. diazotizing agent: nitrites such as sodium nitrite, isoamyl nitrite, t-butyl nitrite, and the like acid: inorganic acids such as tertiary acid luoroboric acid, hydrochloric acid and the like, organic acids such as trifluoromethanesulfonic acid and the like, Lewis acid such as boron trifluoride diethyl etherate and the like. solvent: halogenated aliphatic hydrocarbons such as methylene chloride, chloroform, 1,2-dihydroxyurea, 1,2,3-t ricloropropane and the like, ethers such as diethyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and the like , aqueous hydrochloric acid solution, aqueous hydrobromic acid solution, aqueous sulfuric acid solution and the like, or mixtures of the same. After completion of the reaction, the reaction solution is used in the subsequent reaction as it is, or non-polar organic solvent such as n-pentane, n-hexane and the like, is added to the reaction solution and the precipitate is collected. by filtration, for example. < Step 8-2 > : A process for producing the compound [XIV] of the compound [XXXXVI]. The compound [XIV] can be produced, for example, by reacting the diazonium salt compound [XXXXVI] with the compound [XIII] in a solvent. The reaction temperature is from 0 to 120 ° C, and the reaction time is usually from the first moment to 20 hours. With respect to the amounts of reagents that are reacted, the amount of the compound [XIII] is from 1 mol to 10 mol based on 1 mol of the compound [XXXXVI], however, the proportion can be changed optionally depending on the reaction conditions. Solvent: aromatic hydrocarbons such as toluene and the like, halogenated aliphatic hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane and the like, ethers such as diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether and the like, or mixtures of the same . After completion of the reaction, the present intended compound can be obtained, for example, by the following operation 1) or 2). 1) The reaction solution is poured into water, this is extracted with an organic solvent, and the organic layer is dried and concentrated. 2) The reaction solution is concentrated as is, or, filtered if necessary, and the filtrate is concentrated. In addition, the resulting present compound can also be purified by a method such as chromatography, recrystallization and smem an t e s.
(Production Method 9) "- Of the present compounds, the compound [I] wherein X 1 is nitro (compound [XVI]) or halogen (compound [XVIII]) can be produced by a method shown in the following scheme. [wherein, R1, R2, R3, R15, Q, Y and X2 are the same as defined above, and R25 represents fluorine, chlorine, bromine or iodine.]. < Process 9-l > The compound [XVI] can be produced, for example, by reacting the compound [XV] with the compound [X] in the presence of a base. This reaction is usually conducted without a solvent or in a solvent, and the reaction temperature is from 0 to 200 ° C, and the reaction time is usually from the first time up to 24 hours. reactants that are reacted, it is theoretical that the amount of compound [X] is 1 mole and the amount of the base is 1 mole based on 1 mole of the compound uracil [XV], however, the proportion or amount can be changed optionally depending on the reaction conditions The base to be used includes organic bases such as pyridine, quinoline, benzimide and lamina, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1.5 -diazabicyclo [4.3.0? non-5-ene, 1,4-dia zabicyclo [2.2.2] oct ano, 4-dimethylaminopyridine, N, N -dime ti 1 an i 1 na, N, N-diet i 1-lanyl, triethylamine, tri-n-pr-1-amine, triisopropylamine, tri-n-butylamine, di-op-op-1-1-amine and the like, metal alkoxides such as methoxy or of sodium, sodium ethoxide, potassium t-butoxide and the like, and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium carbonate, sodium carbonate, potassium, sodium hydride, potassium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, and the like. Examples of the solvent to be used include aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether and the like, aromatic hydrocarbons such as benzene, toluene, xylene and the like; halogenated aromatic hydrocarbons such as chlorbenzene, ben z or tri fluo rur and the like; ethers such as diethyl ether, diisopropyl ether, methyl ether 1 - 1 -butene, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme and the like; cotons such as acetone, 2-butanone, methyl isobutyl ketone and the like, esters such as ethyl acetate, butyl acetate and the like, nitriles such as acetonitrile, isomers, and the like, amides such as N, N-dimethylformamide , N, N -dime t ilace tamide, 1-methyl-2-pi rrol idinone and the like; sulfur compounds such as dimethisulfoxide, sulfolane and the like, alcohols such as methanol, ethanol, ethylene glycol, isopropanol, t-butanol and the like, or mixture thereof, thereof. After completion of the reaction, the present compound, intended, for example, by the following operation 1), 2) or 3), can be obtained. 1) The reaction solution is poured into water, this is extracted with an organic solvent, and the organic layer is dried and concentrated. 2) The reaction mixture is poured into water and the precipitate is collected by filtration. 3) The reaction solution is concentrated as is, or, filtered if necessary, and the filtrate is concentrated. . In addition, the resulting present compound can also be purified by a method such as chromatography, r e cr i s t a l i z ation and is exempli ed. < Process 9-2 > The compound [XVII] can be produced, for example, by reducing the compound [XVI] in a solvent. ?) using an iron powder in the presence of an acid, B) with hydrogen in the presence of a catalyst. A) This reaction is usually conducted in a solvent, and the reaction temperature is usually from 0 to 150 ° C, preferably from room temperature to reflux temperature. The reaction time is usually from the first moment up to 24 hours. With respect to the amounts of the reagents that are used in the reaction, the amount of the iron powder is from 3 mol to excess and the amount of the acid is 1 to 10 mol based on 1 mol of the compound [XVI] , however, the proportion or amount may optionally be changed depending on the reaction conditions. As the acid to be used, acetic acid and the like are listed. As the solvent to be used, there are listed, for example, water, acetic acid, ethyl acetate and the like or mixtures thereof. After the completion of the reaction, a desired material can be obtained by a usual operation such as by filtration, then, by pouring a reaction solution into water and the deposited crystals are collected by filtration, or, by extraction with an organic solvent, by neutralization, drying, concentration and the like. B) This reaction is usually conducted in a solvent, the reaction temperature usually being from -20 to 150 ° C, preferably from 0 to 50 ° C. The reaction time is usually from the first instant to 48 hours. This reaction can also be conducted under pressure, and the reaction is preferably carried out under a pressure of 5 atmospheres. The amount of the catalyst used in this reaction is from 0.001 to 10% by weight based on the compound [XVI]. As the catalyst to be used in the reaction, palladium / anhydrous carbon, palladium / carbon containing water, platinum oxide and the like are listed. The solvent includes carboxylic acids such as formic acid, acetic acid, propionic acid and the like, estsuch as ethyl formate, ethyl acetate, butyl acetate and the like, ethsuch as 1,4-dioxane, tetrahydrofuran, dimethyl ether of ethylene glycol and the like, alcohols such as methanol, ethanol and the like, or mixtures thereof and the like. After the termination of the reaction, a desired material can be obtained by a usual operation such as by the filtration of a reaction solution before the concentration of the solution by itself, and similar. The material sought can also be purified by a method such as chromatography, recrystallization and the like. < Process 9-3 > Compound [XVIII] can be produced from compound [XVII], for example, A) by i) diazotization of compound [XVII] in a solvent, then, 1) subsequently it is reacted with halogenating agent in a solvent B) by reacting the compound [XVII] with a diazotizing agent in a solvent in the presence of the halogenating agent. (see, Heterocycles., 38, 1581 (1994) and the like) A) i) In the diazotization reaction of the first step, the reaction temperature is usually from -20 to 10 ° C, and the reaction time is usually from the first moment to 5 hours . With respect to the amounts of reactants that are reacted, it is expected that the amount of the diazotization agent will be 1 mol based on 1 mol of the compound [XVII], however, the proportion or amount may optionally be changed depending on the reaction conditions. As the diazotization agent to be used, nitrites are listed such as sodium nitrite, potassium nitrite, isoamyl nitrite, t-butyl nitrite and the like. As the solvent to be used, there are listed, for example, acetonitrile, hydrobromic acid, hydrochloric acid, sulfuric acid, water and the like or mixtures thereof. The reaction solution after completion of the reaction is used - as it is in the next reaction. ii) In the reaction of the second step, the reaction temperature is usually in a range from 0 to 80 ° C, and the reaction time is usually in a range from a first time to 48 hours. With respect to the amounts of reagents to be used in the reaction, the halogenating agent is from 1 to 3 moles based on 1 mole of the compound [XVII], and the amounts thereof can be optionally changed depending on the condition of reaction. As the halogenation agent used, potassium iodide, copper (I) bromide (or mixture with copper (II) bromide), copper (I) chloride (or mixture with copper (II) chloride) or a mixture of hydrofluoric acid and boric acid (mentioned below, referred to as hydroborofloric acid) and the like. As the solvent to be used, there are listed, for example, acetonitrile, diethyl ether, hydrobromic acid, hydrochloric acid, sulfuric acid, water and the like or mixtures thereof. After completion of the reaction, a present compound intended, for example, by the following treatment can be obtained; The reaction solution is poured into water and if necessary acid such as hydrochloric acid, it is extracted with an organic solvent, and the resulting organic layer is dried and concentrated. (see, Org Syn. Col. Vol. 2, 604 (1943), Vol. 1, 136 (1932)) B) the reaction temperature is usually from -20 to 50 ° C, preferably from -10 ° C at room temperature, and the reaction time is usually from the first time up to 48 hours. With respect to the amounts of reagents that are reacted, the amount of the halogenating agent is from 1 mol to 3 mol, the amount of the diazotization agent is from 1 mol to 3 mol r esp cti va in te, based on 1 mol of the compound [XVII], however, the ratio can be optionally changed depending on the reaction conditions. As the halogenation agent used, for example, iodine, copper (I) bromide (or mixture with copper (II) bromide), copper (I) chloride (or mixture with copper (II) chloride) are listed. ) or hydrolytic acid of 1 socor and the like.
As the diazotization agent to be used, nitrites such as isoamyl nitrite, t-butyl nitrite and the like are listed. As the solvent to be used, there are listed, for example, ketonitrile, benzene, toluene and the like or mixtures thereof. After completion of the reaction, a present compound intended, for example, by the following treatment can be obtained; the reaction solution is poured into water, and if necessary acid such as hydrochloric acid is added, then it is extracted with an organic solvent, and the resulting organic layer is dried and concentrated. In addition, the resultant present compound can also be purified by a method such as chromatography, r e cr i s t a l i ation and s eme before.
(Production Method 10) Of the present compounds, the compound (I) wherein X1 is cyano (compound [10-3]) can be produced by a method shown in the following scheme wherein R1, R2, R3, 'Q, X2 and Y are the same as defined above, X10 is bromine or iodine, and M1 represents a metal such as copper, potassium, sodium, and the like. The compound [10-3] can be produced by reacting the compound [10-1] with the compound [10-2]. This reaction is usually carried out in a solvent. The reaction temperature is usually in a range from 130 to 250 ° C, preferably at 150 ° C up to the reflux temperature and the reaction time is usually from the first moment to 24 hours. The compound [10-2] used in the reaction includes copper cyanide, potassium cyanide, sodium cyanide and the like. The amount of the compound [10-2] is in a proportion from 1 mole to the amount of excess, pre fer ibl e in t from 1 to 3 moles based on 1 mole of the compound [10-1], however, the ratio it can be optionally changed depending on the reaction conditions. Examples of the solvent to be used include ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme and the like; amides such as N, N-dimethy1-formamide, N, N-dimethoxymethyl, N-methyl-2-pyrrolidone and the like; sulfur compounds such as dimethyl sulfoxide, sulfolane and the like; or mixtures thereof. After completion of the reaction, an object compound can be obtained, for example, by subjecting the ordinary one to the treatment by the following procedure. 1) The reaction mixture is filtered and concentrated. 2) The reaction mixture is added to water, extracted with an organic solvent, washed with water, dried and concentrated. In addition, the subject compound can also be purified by a method such as chromatography, re cr i s t a 1 i z ation and the like. The compound [IV], composed of alcohol [VI], composed of alcohol [VIII], compound [X], compound [XIII], compound [XV], - compound [XXXX], compound [XXXXII], compound [XXXXIII] , compound [XXXXIV] used in the production methods of the present compound are commercially available, or can be produced by known methods. ' The compound [IX] is known, for example, from DE4412079 A. The carboxylic acid compound [VII] can be produced by acidolysis of the present compound [I] wherein the corresponding site is an ester. The compound [XI] is known, for example, from JP-A Nos. 63-41466, 61-40261 and WO9847904, or it can be produced according to the methods in these publications. Some production intermediaries used in the production methods of the present compound can be produced, for example, by the following (Intermediary Production Method 1) to (Intermediary Production Method 2).
(Production Method of I n t e rmedi ar i 12 Compound [XII] where R3 is OR7, SR8 or N (R9) R10 can be produced by a method shown in the following scheme (wherein, R26 represents a separation group such as fluorine, chlorine, bromine, iodine, methylene glycol, pyrrolidone and the like, R11, R16, Q and are the same as defined above.] The compound [XI-2] can be produced, for example, by reacting the compound [Xl-1] with the compound [XIII] in a solvent, in the presence of a base. reaction, for example, is as follows: Reaction temperature: from 0 to 180 ° C Reaction time: from the first moment to 24 hours The amount of the compound [XIII]: from 1 mol to 1.5 mol based on 1 mol of the compound [Xl-1] The amount of the base: from 1 mole to 1.5 mole based on 1 mole of the compound [Xl-1] However, the ratio or proportion can optionally be changed depending on the reaction conditions. Base: triethylamine, diisopropylethylamine, potassium carbonate, sodium hydride and the like. Solvent: dioxane, tetrahydrofuran, N, N -dime t i 1 f or rmami da, 1 -me t i 1 -2 -p i r r ol ol idonona y s eme jantes. After completion of the reaction, the intended compound can be obtained, for example, by the following treatment; The reaction solution is poured into water, this is extracted with an organic solvent, and the organic layer is dried and concentrated. In addition, the resulting compound can also be purified by a method such as chromatography and the like.
(Production Method of I n t e rmedi a r i o 2 Compound [III] where is NH (compound [XXIII]) can be produced by a method shown in the following scheme [X I I 1] [wherein, R1, R2, R16, Y, Q, X1 and X2 have the same meaning as described above.]. < Process A2-A1 > : A process for producing the compound [XXII] from the compound [XI]. The compound [XXII] can be produced by reacting the compound [XI] with the compound [XXI] in the presence of a base. This reaction is usually conducted without a solvent or in a solvent, and the reaction temperature is in a range from 0 to 200 ° C, and the reaction time is usually in a range from a first time to 24 hours. With respect to the amounts of reactants that are reacted, it is theoretically the amount of the compound [XXI] is 1 mole and the amount of the base is 1 mole based on 1 mole of the compound [XI], the proportion can be changed optionally depending on the reaction conditions. Base: triethylamine, diisopropylethylamine, potassium carbonate, sodium hydride, sodium hydroxide and the like before. Solvent: toluene, dioxane, tetrahydrofuran, N, N-d ime t i 1 or rmamide, 1-methyl-2-pi r rol idinone, dimethisulfoxide, sulfolane and the like, or mixtures thereof. This reaction can sometimes be accelerated by the addition of a catalyst. The preferable amount of the catalyst to be used in the reaction is from -0,0001 to 0.1 ol based on 1 mole of the compound [XI], and this ratio can optionally be changed depending on the reaction conditions. As the catalyst, copper compounds such as copper iodide, copper bromide, copper chloride, copper powder and the like, and crown ethers such as 15-crown-5, 18-crown-6 and similar. After completion of the reaction, a desired compound can be obtained, for example, by the following treatment: the reaction solution is poured into water, this is extracted with an organic solvent, and the organic layer is dried and concentrated. A desired compound can also be purified by an operation such as chromatography, recrystallization and the like. < Process A2-2 > : A process for producing the compound [XXIII] from a compound [XXII]. The compound [XXIII] can be produced, for example, reducing the compound [XXII] in a solvent, A) using an iron powder in the presence of an acid. B) with hydrogen in the presence of a catalyst. A) The reaction temperature is usually from 0 to 150 ° C, preferably from room temperature to reflux temperature. The reaction time is usually from the first moment up to 24 hours. With respect to the amounts of reactants to be used in the reaction, the amount of the iron powder is from 3 mol to excess and the amount of the acid is from 1 to 10 mol based on 1 mol of the compound [XXII], however, the ratio can be changed optionally depending on the reaction conditions. As the acid to be used, acetic acid and the like are listed. As the solvent to be used, there are listed, for example, water, acetic acid, ethyl acetate and the like or mixtures thereof. After completion of the reaction, a desired material can be obtained by a usual post-treatment operation such as filtration, then, by pouring a reaction solution into water and collecting the crystals deposited by filtration, or extraction with an organic solvent, neutralization, drying, concentration and the like. B) The reaction temperature is usually from -20 to 150 ° C, preferably from 0 to 50 ° C. The reaction time is usually from the first moment up to 48 hours. This hydrogenation reaction can also be conducted under pressure, and the reaction is preferably conducted under a pressure of 1 to 5 atoms. The amount of the catalyst used in this reaction is from 0.01 to 10% by weight based on the compound [XXII]. As the catalyst to be used in the reaction, palladium / carbon, platinum oxide and the like are listed. The solvent includes acetic acid, ethyl acetate, methanol, ethanol and the like, or mixtures thereof. After the completion of the reaction, a intended material can be obtained by a usual post-treatment operation such as filtering a reaction solution before the concentration of the solution by itself, and the like. The intended compound can also be purified by an operation such as chromatography, recrystallization and the like.
(Intermediary Production Method 3) Compounds [III] where W is oxygen (compound [V]) can be produced by a method shown in the following scheme [where, R1, R2, Y, Q, X1 and X2 are the same as previously defined.]. The compound [V] can be produced i) by reacting the compound [XXIII] with a diazotization agent in a solvent, in the presence or absence of an acid, then, ii) subsequently, heating the reaction product in an acidic solvent or allowing a copper salt to act on the reaction product in the presence or absence of a copper catalyst. i) In the reaction of the first step, the reaction temperature is in a range from -20 to 10 ° C and the reaction time is usually in a range from the first moment to 5 hours. With respect to the quantities of reactants to be reacted, it is theoretically necessary that the amount of the diazotization agent be 1 mol and the amount of the acid be 1 mol based on 1 mol of the compound [XXIII], however, the proportion can be changed optionally depending on the reaction conditions. As the diazotization agent used, there are listed, nitrite such as sodium nitrite, potassium nitrite, isoamyl nitrite, t-butyl nitrite and the like. As the acid used, there are listed, for example, tetrahydric acid, hydrochloric acid, trifluoromethanesulfonic acid, Lewis acid such as boron trifluoride diethyl etherate, and the like.
As the solvent used, there are listed, for example, halogenated aliphatic hydrocarbon such as methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,2,3-t-ricloropropane and the like, ethers such as diethyl ether. diisopropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran, • dimethylether of ethylene glycol, diglyme and the like, acetonitrile, aqueous hydrochloric acid solution, aqueous hydrobromic acid solution, aqueous sulfuric acid solution and the like, or mixtures thereof. The reaction solution after completion of the reaction is used in the subsequent reaction as it is, for example. ii) In the reaction in which the heating is conducted in an acidic solvent, in the second step, the reaction temperature is in a range from 60 ° C to the reflux heating temperature, and the reaction time is usually in a range from the first moment to 24 hours. As the acid solvent, there are listed, for example, aqueous hydrochloric acid solution, aqueous hydrobromic acid solution, aqueous sulfuric acid solution and the like. After completion of the reaction, a desired material can be obtained, for example, by subjecting the reaction solution to customary reactions such as filtration of a reaction solution, extraction with an organic solvent, drying , concentration and similar. (see, Org. Syn. Coll. • Vol. 2, 604 (1943), Vol. 1, 136 (1932)) The reaction in which the copper salt is allowed to act in the presence or absence of the copper catalyst, in the second step, is conducted in a solvent, the reaction temperature is in a range from 0 ° C to the reflux heating temperature, and the reaction time is usually in a range from the first moment to 24 hours. With respect to the amounts of reagents that are reacted, the amount of the copper catalyst is from 0.001 to 5 mol and the amount of the copper salt is from 1 to 100 mol based on 1 mol of the compound [XXIII], however , the proportion can be optionally changed depending on the reaction conditions. As the copper catalyst used, copper (I) oxide and the like are listed, and copper salt (II), copper (II) nitrate, and the like are listed as the copper salt. As the solvent, water, aqueous hydrochloric acid solution, aqueous sulfuric acid solution, acetic acid and the like, or mixtures thereof, are listed by e. After the completion of the reaction, a desired or intended compound can be obtained, for example, by subjecting the reaction solution to usual procedures such as filtration of a reaction solution, neutralization, extraction with organic solvent, drying, concent ration and s eme jantes. The desired compound can also be purified by an operation such as chromatography, recrystallization and the like.
Production Method of the Intermediary 4 The compound [X] wherein R3 is OR7 or SR8 (compound [XXVI]) can be produced by a method shown in the following scheme [XXV] [IV] [XXVI] [wherein, R 11, R 12, Y and Q are equal-1 as defined above, and R 17 represents oxygen or sulfur]. The compound [XXVI] can be produced by reacting the compound [XXV] with the compound [IV] in the presence of a base. This reaction is usually conducted in a solvent, and the reaction temperature is usually in a range from 0 to 150 ° C, and the reaction time is usually in a range from the first time to 24 hours. With respect to the amounts of reagents that are reacted, it is theoretically that the amount of the compound [IV] is 1 mole and the amount of the base is 1 mole based on 1 mole of the compound [XXV], however, the The proportion can optionally be changed depending on the reaction conditions. As the base used, organic bases are listed such as pyridine, 4-dimethylaminopyridine, N, -dimethe 1-ani-1-one, N, N-diethylamino-1, -'-triethylamine, diisopropylethylamine and the like, and inorganic bases such as carbonate of sodium, potassium carbonate, sodium hydride, sodium hydroxide, potassium hydroxide, and similar before. As the solvent used, there are listed, for example, aromatic hydrocarbons such as toluene, xylene and the like, aromatic halogenated hydrocarbons such as chlorobenzene, ben zotrif 1 or ro roy, ethers such as diethyl ether, dioxane, tet rah i dro fur anus , ethylene glycol dimethyl ether and the like, ketones such as acetone, 2-butanone, methyl isobutyl ketone and the like, esters such as ethyl acetate and the like, nitriles such as acetonitrile and the like, amides such as N, N-dime ti 1 f ormami da, N -me ti 1 -2 -pirro 1 i donates and the like, sulfur compounds such as dimethisulfoxide and the like, alcohols such as methanol, ethanol and the like, - or mixtures thereof. "After completion of the reaction, a desired compound can be obtained, for example, by the following operation 1) or 2): 1) The reaction solution is poured into water, this is extracted with an organic solvent, and the The organic layer is dried and concentrated 2) The reaction solution is concentrated as it is, or filtered if necessary, and the filtrate is concentrated.The desired compound can also be purified by an operation such as chromatography, reaction 1. iza ci on and similar.
(Intermediary Production Method 5) The compound [X] wherein R3 is OR7, SR8 or N (R9) R10, and Y is oxygen or sulfur (compound [XXX]) can be produced by a method shown in the scheme following.
[XX [wherein, R11, R12, R17, W and Q are the same as defined above, and R19 represents a protecting group such as t-bu ti ldime ti ls i 1 i lo, t-butyl, benzyl, methyl eme j before]. < Process A5-l > : A process for producing the compound [XXVIII] from the compound [XXVII]. Compound [XXVIll] can be produced by reacting compound [XXVII] with t -bu ti 1 dimethyl ti 1 chloride, isobutene, benzyl chloride, benzyl bromide or the like (see, "Yuki Kagaku Jikken no Tebiki "vol.4, (published by KagakuDojin), Protective Groups in Organic Synthesis (published by JOHN ILEY &SONS, INC.)). < Process A5-2 > : A process for producing the compound [XXIX] from the compound [XXVIII].
The compound [XXIX] can be produced by reacting the compound [XXVIII] with the compound [IV] in the presence of a base. This reaction is usually conducted in a solvent, and the reaction temperature is usually in a range from 0 to 150 ° C, and the reaction time is usually in a range from the first time to 24 hours. With respect to the quantities of reagents that are reacted, it is theoretically the amount of the compound [IV] to be 1 mol and the amount of the base to be 1 mol based on 1 mol of the compound [XXVIII], however, the The proportion can optionally be changed depending on the reaction conditions. As the base used, organic bases are listed such as pyridine, 4-dimethylaminopyridine, N, N-dime thiol, 1 N, N, N-di ti lani-1-one, triethylamine, diisopropylethylamine and the like, and inorganic bases such as sodium carbonate. sodium, potassium carbonate, sodium hydride, sodium hydroxide, potassium hydroxide, and so on.
As the solvent used, aromatic hydrocarbons such as toluene, xylene and the like are listed, aromatic halogenated hydrocarbons such as chlorobenzene, benzot ri fluoride and the like, ethers such as diethyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and similar, ketones such as acetone and the like, esters such as ethyl acetate and the like, nitriles such as acetonitrile, isobutylium and the like, amides such as N, N-dimethylammonium, N-me ti 1 -2-Pi 1 -one and the like, sulfur compounds such as dimethisulfoxide and the like, alcohols such as methanol, ethanol and the like, or mixtures of the same. After completion of the reaction, a desired compound can be obtained, for example, by the following operation 1) or 2). 1) The reaction solution is poured into water, this is extracted with an organic solvent, and the organic layer is dried and concentrated. 2) The reaction solution is concentrated as is, or filtered if necessary, and the filtrate is concentrated.
The desired compound can also be purified by an operation such as chromatography, recrystallization and the like. < Process A5-3 > : A process for producing compound [XXX] from compound [XXIX]. Compound [XXX] can be produced by deprotection of compound [XXIX], for example, according to a method described in "Yuki Kagaku Jikken no Tebiki" vol. 4, (published by Kagaku Dojin), Protective Groups in Organic Synthesis (published by JOHN ILEY &SONS, INC.).
(Intermediary Production Method ß) Compound [III] where it is oxygen (compound [V]) can be produced by a method shown in the following scheme: i] [XXXXVE] [wherein, R1, R2, A ", Y, Q, X1 and X2 are the same as defined above, R34 represents alkyl such as methyl and the like, or haloalkyl such as trifluoromethyl and imi res.]. < Step A6-l > : A process for producing the compound [XXXXVIII] from the compound [XXXXVI].The compound [XXXXVIII] can be produced, for example, by reacting the diazonium salt compound [XXXXVI] with the compound [XXXXVII]. This reaction is usually conducted without a solvent or in a solvent, the reaction temperature is from room temperature to 120 ° C, preferably from 50 to 90 ° C, and the reaction time is usually from an instant to 5 hours . With respect to the amounts of the reactants to be reacted, the amount of the compound [XXXXVI] is from 1 mole to excess based on 1 mole of the compound - [XXXXVI], however, the proportion can be optionally changed depending on the conditions of reaction. Like the solvent used, acetic acid and imi res, After completion of the reaction, the proposed compound can be obtained, for example, by the following treatment; The reaction solution was concentrated as it was, the residue was diluted with water, this was extracted with an organic solvent, and the organic layer was dried and concentrated. In addition, the resulting compound can also be purified by a method such as chromatography, re-cryssation and imi res ion. < Step A6-2 > : A process for producing the compound [V] from the compound [XXXXVIII].
The compound [V] can be produced, for example, by reacting the compound [XXXXVIII] in the presence of a base in a solvent.
The reaction temperature is from 0 to 100 ° C, preferably from room temperature to 60 ° C, and the reaction time is usually from 0.5 to 20 hours.
With respect to the amounts of the reactants to be reacted, the amount of the base is from 0.1 mol 10 mol based on 1 mol of the compound [XXXXVIII], however, the proportion can be optionally changed depending on the reaction conditions . As the base used, these are listed inorganic bases such as sodium carbonate, potassium carbonate, sodium acid carbonate and the like. As the solvent used, for example, these are listed, methanol, ethanol water and the like, or mixtures thereof. After completion of the reaction, the proposed compound can be obtained, for example, by following the treatment; the reaction solution was concentrated as it was, the residue was diluted with water, this was extracted with an organic solvent, and the organic layer was dried and concentrated. In addition, the resulting compound can also be purified by a method such as chromatography, recrystallization and the like.
(Intermediary Production Method 7) The compound [XXXI] can be produced by a method shown in the following scheme. [wherein, R1, R3, R15, Y, Q, X1 and X2 are the same as defined above, and R18 represents lower alkyl such as methyl, ethyl and the like, R27 represents alkyl of 1 to 6 carbon atoms such as methyl, ethyl and. similar, or phenyl which can be substituted such as phenyl and the like. ] < Step A7-l > : A process for producing the compound [XXXXXI] from the compound [XXXXX] The compound [XXXXXI] can be produced, for example, by reacting the compound [XXXXX] with the compound [X] in the presence of a base. This reaction is usually conducted without a solvent or in a solvent, the reaction temperature is usually in a range from 0 to 150 ° C, and the reaction time is usually in a range from an instant to 48 hours. With respect to the amounts of reactants to be reacted, it is theoretical that the amount of the compound [X] is 1 mole and the amount of the base is 1 mole based on 1 mole of the compound [XXXXX], however, the proportion can be be 'optionally changed depending on the reaction conditions.
As the base used, are the listed organic bases such as pyridine, N, N-dimethylaniline, N, N-diethylaniline, triethylamine, diisopropylethylamine and the like, metal alkoxides such as sodium methoxide, sodium ethoxide, tert-butoxide potassium and similar, and inorganic bases such as potassium carbonate, sodium acid carbonate, sodium hydride, lithium hydroxide, sodium hydroxide and imides. As the solvent used, there are listed, for example, aromatic hydrocarbons such as toluene, xylene and the like, ethers such as dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and the like, ketones such as acetone, 2-butanone, methyl isobutyl ketone and the like, esters such as ethyl acetate, and the like, nitrile such as acetonitrile, is obut ironi tri lo and the like, amides such as, N, N-dimethylformamide, and the like, sulfur compounds such as dimethisulfoxide and the like, alcohols such as methanol, ethanol and the like, or mixtures thereof. After completion of the reaction, the proposed compound can be obtained, for example, by the following operation 1) or 2). 1) The reaction solution was poured into water, this was extracted with an organic solvent, and the organic layer was dried and concentrated. 2) The reaction solution was concentrated as it is, or, filtered if necessary, and the filtrate was concentrated.
The resulting present compound can also be purified by an operation such as chromatography, recrystallization and the like. < Step A7-2 > : A process for producing the compound [XXXXXIII] from the compound [XXXXXI] The compound [XXXXXIII] can be produced by reacting with isocyanate the compound [XXXXXI] in a solvent or without a solvent. Isocyanation agent: phosgene, trichloromethyl chloroformate, triphosgene, oxalyl chloride and the like.
The amount of the isocyanate agent: from 1 mole to the excess, preferably from 1.0 to 3 mole based on 1 mole of the compound [XXXXXI]. Solvent: aromatic hydrocarbons such as benzene, toluene and the like, halogenated aromatic hydrocarbons such as chlorobenzene and the like, esters such as ethyl acetate and similar. The reaction temperature: from room temperature to reflux temperature. Reaction time: from * an instant to 48 hours. This reaction can be accelerated sometimes by adding a catalyst. The amount of the catalyst used in this reaction is from 0.001 to 300% by weight based on the compound [XXXXXI], and the amounts thereof can optionally be changed depending on the reaction condition. As the catalyst, carbon (activated), amines such as triethylamine and the like are listed. After completion, a proposed material can be obtained by concentrating a reaction solution of itself, and the like.
This compound can also be purified by an operation such as re-crystallization and the like. < Process A7-3 > : A process for producing the compound [XXXXXII] from the compound [XXXXXI] The compound [XXXXXII] can be produced by reacting the compound [XXXXXI] with a compound [a7-l] of the formula [a7-l] [wherein, R27 is the same as defined ant eriorment e, and X12 represents fluorine, chlorine, bromine or iodine. ] in the presence of a base. This reaction is usually conducted in a solvent, and can also be conducted without a solvent. The reaction temperature is usually from -20 to 200 ° C. The reaction time is usually from an instant to 48 hours. The amount of the compound [a7-l] used in the reaction is from 0.5 mol to excess, preferably from 1.0 to 1.2 mol based on 1 mol of the compound [XXXXXI]. The amount of the base used in the reaction is from 0.5 mol to excess, preferably from 1.0 to 1.2 mol based on 1 mol of the compound [XXXXXI]. The base includes inorganic bases such as sodium carbonate, sodium hydroxide and the like, organic bases such as pyridine, 4-dimethylaminopyridine, N, N-dimethylamino, N, N-diethylaniline, triethyl. lamí na, diisopropilamina and imi lares. The solvent includes aliphatic halogenated hydrocarbons such as chloroform and the like, ethers such as tetrahydrofuran, 1,4-dioxane, and the like, nitriles such as ce t oni tary and similar, esters such as ethyl acetate, water or mixtures thereof. same, and imi lares. After completion of the reaction, a proposed material can be obtained by such a usual post-treatment operation. such as filtering the reaction solution before concentrating the solution by itself, or, pouring the reaction solution into water and collecting the crystals produced by filtration, or, pouring the reaction solution into water and subjecting the mixture to water. the extraction with an organic solvent, drying, concentration and the like. This compound can also be purified by an operation such as recrystallization, chromatography and the like. < Process A7-4 > : A process for producing compound [XXXI] from compound [XXXXXIII] The compound [XXXI] can be produced by reacting the compound [XXXXXIII] with the compound [XXXXXIV] in a solvent in the presence of a base. The amount of the compound [XXXXXIV]: 0.5 mol to excess, preferably from 0.8 to 1.2 mol based on 1 mol of the compound [XXXXXIII]. Base: inorganic bases such as sodium hydride and the like, metal alkoxides such as sodium methoxide, sodium ethoxide and the like. Base amount: 0.5 mol to excess, preferably from 0.8 to 1.2 mol based on 1 mol of the compound [XXXXXIII]. Solvent: aromatic hydrocarbons such as benzene, toluene and the like; halogenated aromatic hydrocarbons such as chlorobenzene and the like; amides such as N, N-dime t i 1 formamide and the like; ethers such as tetrahydrofuran and the like; halogenated aliphatic hydrocarbons such as chloroform and the like; sulfur compound such as dimethyl sulfoxide and the like; and mixtures thereof. Reaction temperature: -40 ° C to reflux temperature of the solvent Reaction time: instant to 72 hours After completion of the reaction, a proposed material can be obtained by a post-treatment operation such as by filtering a reaction solution before concentrating the solution by itself, or adding an acid to a reaction solution and collecting the crystals produced by filtration by adding an acid to a reaction solution, then, subjecting the mixture to extraction with an organic solvent, concentration and the like. As the acid to be added, hydrochloric acid, acetic acid, trifluoroacetic acid, p-toluenesulfonic acid, or aqueous solutions thereof and the like. This compound can also be purified by an operation such as re-crystallization, chromatography and the like.
The resulting compound [XXXI] can also be reacted with the compound [XXXX] according to a method described in (Production Method ß) without the aforementioned post-treatment conduction, to produce the present compound. < Process A7-5 > : A process to produce compound [XXXI] from compound [XXXXXII] The compound [XXXI] can be produced by reacting the compound [XXXXXII] with the compound [XXXXXIV] in the presence of a base. This reaction is usually conducted in a solvent, and the reaction temperature is usually from -20 to 200 ° C, preferably from 0 to 130 ° C. The reaction time is usually from an instant to 72 hours. The amount of the compound [XXXXXIV] used in the reaction is from 0.5 mol to excess, preferably from 0.8 to 1.2 mol based on 1 mol of the compound [XXXXXII]. The amount of the base used in the reaction is from 0.5 mol to excess, preferably from 0.8 to 1.2 mol based on the compound [XXXXXII]. The base includes organic bases such as 4-dimime ti laminopyr idine, diisopropylamine and the like, inorganic bases such as sodium carbonate, potassium carbonate, sodium hydride, potassium hydride and the like, metal alkoxides such as sodium methoxide, ethoxide sodium, potassium t-butoxide and the like. The solvent includes ketones such as acetone, methyl isobutyl ketone and the like; aliphatic hydrocarbons such as hexane, heptane, petroleum ether and the like; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, methylene and the like; ethers such as diethyl ether, diisopropyl ether, 1, -dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, me ti 1-t -bu t i 1 ether and the like; acidic amides such as N, N -dimethyl-il-ormamide, N, N-dimethylacetamide and the like; tertiary amines such as pyridine, N, N-dimethoxylane, N, N-di e t i lani-1a, triethylamine, diisopropylethylamine and the like; sulfur compounds such as dimethyl sulfoxide, sulfolane and the like; or mixtures thereof and imi iers. After the completion of the reaction, a proposed material can be obtained by a usual post-treatment operation such as by filtering the reaction solution before the concentration of the solution by itself, or, by adding an acid to the reaction solution and collecting the crystals produced by filtration, or, adding an acid to the reaction solution, then, subjecting the mixture to extraction with an organic solvent, with cen tration. and similar.
As the acid to be added, hydrochloric acid, acetic acid, trifluoroacetic acid, p-toluenesulfonic acid, or aqueous solutions thereof and the like are listed. This compound can also be purified by an operation such as recrystallization, chromatography or the like. The resulting compound [XXXI] can also be reacted with the compound [XXXX] according to the method described in (Production Method 6) without the post-treatment conduit mentioned above, to produce the present compound.
(Intermediary Production Method 8) Compound [X] can be produced where Y is oxygen, Q is a pyridine ring, and R3 is OR-7, SR8 or N (R9) R10 (compound [XXXXXX]) by a method shown in the following scheme. [xxxxxvj Ex ???? vj] CXXXXXVII] [wherein R11, R12, R24, Z1, Z2, W and A are the same as defined above]. < Step A8-l > : Compound [XXXXXVI] can be produced, for example, by reacting compound [XXXXXV] with compound [XIII] in the presence of a base. This reaction is usually conducted without a solvent or in a solvent, and the reaction temperature is from 0 to 200 ° C, and the reaction time is usually from one instant to 48 hours. Considering the quantities of reactants to be reacted, it is theoretically that the amount of compound [XIII] is 1 mol and the amount of the base is 1 mol based on 1 mol of the compound [XXXXXV], however, the proportion can optionally be changed depending on the reaction conditions. The base to be used includes organic base such as pyridine, quinoline, 1,8-diazabicyclo [5.4.0] undec-7-ene, 4-dimethylaminopyridine, N, N-dimethylaniline, N, N-diethylaniline, triethylamine, diisopropylethylamine and similar, and inorganic bases such as lithium carbonate, potassium carbonate, sodium hydride, potassium hydride, lithium hydroxide, sodium hydroxide and the like. Examples of the solvent to be used include aromatic hydrocarbons such as toluene, xylene and the like; aromatic halogenated hydrocarbons such as benzotrifluoride and the like; ethers such as tetrahydrofuran, ethylene glycol dimethyl ether and the like; ketones such as acetone, 2-butanone, methyl isobutyl ketone and the like; esters such as ethyl acetate, butyl acetate and the like; nitriles such as acetonitrile, isobutyronitrile and the like; amides such as N, N-dimethylformamide, N, N-dimethylacetamide, l-methyl-2-pyrrolidinone and the like; sulphurous compounds such as dimethyl sulfoxide, sulfolane and the like or mixtures thereof. After completion of the reaction, the compound proposed can be obtained, for example, by the following operation 1), 2) or 3). 1) The reaction solution is poured into water, this is extracted with an organic solvent, and the organic layer is dried and concentrated. 2) The reaction mixture is poured into water and the precipitate is collected by filtration. 3) The reaction solution is concentrated as such, or filtered if necessary, and the filtrate is concentrated. In addition, the resulting present compound can also be purified by a method such as chromatography, re-crystallization and the like. < Stage A8-2 > : Compound [XXXXXVII] can be produced, for example, by reducing compound [XXXXXVI] in a solvent, A) using an iron powder in the presence of an acid, B) with hydrogen in the presence of a catalyst.
A) This reaction is usually conducted in a solvent, and the reaction temperature is usually from 0 to 100 ° C, preferably from room temperature to reflux temperature. The reaction time is usually from one instant to 48 hours. Considering the amounts of reactants to be used in the reaction, the amount of the iron powder is 3 mol to excess and the amount of the acid is 1 to 10 mol based on 1 mol of the compound [XXXXXVI], however, the ratio it can be optionally changed depending on the reaction conditions. As the acid to be used, acetic acid and the like are listed. As the solvent to be used, there are listed, for example, water, acetic acid, ethyl acetate and the like or mixtures thereof. After completion of the reaction, a proposed material can be obtained by a usual post-treatment operation, such as filtration, then, by pouring a solution of the reaction into water and collecting the deposited crystals by filtration, or, extraction with a solvent organic, neutralization, drying, concentration and the like.
B) This reaction is usually conducted in a solvent. The reaction temperature is usually from -20 ° C to 150 ° C, preferably from 0 to 50 ° C. The reaction time is usually from one instant to 48 hours. This reaction can also be conducted under reduced pressure, and the reaction is preferably conducted under a pressure of 1 to 5 atoms. The amount of catalyst used in this reaction is from 0.001 to 10% by weight based on the compound [XXXXXVI]. As the catalyst to be used in the reaction, palladium / anhydrous carbon, palladium / carbon containing water, platinum oxide and the like are listed. The solvent includes carboxylic acids such as formic acid, acetic acid, propionic acid and the like, esters such as ethyl acetate, butyl acetate, and the like, alcohols such as methanol, ethanol and the like, or mixtures thereof and the like. After completion of the reaction, a proposed material can be obtained by a usual post-treatment operation such as filtering a reaction solution before concentration of the solution itself and the like. The proposed material can also be purified by a method such as chromatography, re-crystallization and the like. < Stage A8-3 > : Compound [XXXXXVIII] can be produced, for example, by reacting compound [XXXXXVII] with a diazotizing agent and an acid in a solvent. The reaction temperature is from -30 ° to 30 ° C, and the reaction time is usually from an instant to 5 hours. Considering the quantities of reactants to be reacted, the amount of the diazotizing agent is from 1 mol to 3 mol, and the amount of acid is from 1 mol to 6 mol based on 1 mol of the compound [XXXXXVII], however, the proportion it can be optionally changed depending on the reaction conditions. As the diazotizing agent used, there are listed, for example, nitrites such as sodium nitrite, isoamyl nitrite, t-butyl nitrite, and the like.
As the acid used, there are listed, for example, organic acids such as tetrafluoroboric acid, hydrochloric acid and the like, organic acids such as trifluoromethanesulfonic acid and the like, acid, lewis such as boron trifluoride diethyl etherate and the like. As the solvent used, there are listed, for example, aliphatic halogenated hydrocarbons such as methylene chloride, chloroform, 1,2-dichloroethane, 1,2,3-trichloropropane and the like, ethers such as diethyl ether, dioxane, tetrahydrofuran, dimethyl ether ethylene glycol, and the like or mixtures thereof. After completion of the reaction, the reaction solution is used in the subsequent reaction as such, or non-polar organic solvent such as n-pentane, n-hexane and the like are added to the reaction solution and the precipitate it is collected by filtration, for example. < Stage A8-4 > : Compound [XXXXXIX] can be produced, for example, by reacting the diazonium salt [XXXXXVIII] with the compound [XXXXVII]. This reaction is usually conducted without a solvent or in a solvent, the reaction temperature is from room temperature to 120 ° C, preferably from 50 to 90 ° C, and the reaction time is usually from an instant to 5 hours. Considering the reactants to be reacted, the amount of the compound [XXXXVII] is 1 mol to excess, based on 1 mol of the compound [XXXXVII], however, the proportion can be optionally changed depending on the reaction conditions. As the solvent used, acetic acid and the like. After the completion of the reaction, the proposed compound can be obtained, for example, by the following treatment; the reaction solution is concentrated as such, the residue is diluted with water, this is extracted with an organic solvent, and the organic layer is dried and concentrated. In addition, the resulting compound can be purified by a process such as chromatography, re-crystallization and the like. < Stage A8-5 > : Compound [XXXXXX] could be produced, for example, by reacting compound [XXXXXIX] in the presence of a base in a solvent. The reaction temperature is from 0 to 100 ° C, preferably from room temperature to 60 ° C, and the reaction time is usually from 0.5 to 20 hours. Considering the amounts of reactants to be reacted, the amount of the base is from 0.1 mol to 10 mol based on 1 mol of the compound [XXXXXIX], however, the proportion can be optionally changed, depending on the reaction conditions. As the base used, the inorganic bases such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate and the like are listed. As the solvent used, for example, methanol, ethanol, water and the like, or mixtures thereof, are listed. After the completion of the reaction, the proposed compound can be obtained, for example, by the following treatment; the reaction solution is concentrated as such, the residue is diluted with water, this is extracted with an organic solvent, and the organic layer is dried and concentrated. In addition, the resulting compound can also be purified by a method such as chromatography, re-crystallization and the like.
(Intermediary Production Method 9) The compound [X] where Y is oxygen, Q is a pyrimidine ring, and R3 is OR7, SR8 or N (R9) (R10) (compound [19-4]) can be produced by a method shown in the following scheme. [wherein, R11, R19, R25, and Z1 are as defined above]. < Step A9-10: Compound [19-2] can be produced, for example, by reacting the compound [19-1] with a halogenating agent, without a solvent or in a solvent.
Reaction temperature: 50 ° C at reflux temperature. Reaction time: from one instant to 36 hours. Halogenation agent: phosphorus oxybromide, phosphorus oxychloride and the like. The amount of the halogenating agent: from 1 mole to excess based on 1 mole of the compound [19-1]. However, the proportion can optionally be changed depending on the reaction conditions. Solvent: toluene and the like. After the completion of the reaction, the proposed compound can be obtained, for example, by the following treatment; the reaction solution is concentrated as such, the residue is diluted with water, this is extracted with an organic solvent, and the organic layer is dried and concentrated. In addition, the resulting compound can also be purified by a method such as chromatography, recrystallization and the like. < Stage A9-2 > The compound [I9-a] can be produced, for example, by reacting the compound [19-2] with the compound [XIII] in a solvent, in the presence of a base. Reaction temperature: from 0 to 180 ° C. Reaction time: from an instant to 24 hours. The amount of the compound [XIII]: from 1 mol to 1.5 mol based on 1 mol of the compound [19-2]. The amount of the base: from 1 mol to 1.5 mol based on 1 mol of the compound [19-2]. Nevertheless, the proportion can be optionally changed depending on the reaction conditions. Base: triethylamine, diisopropylethylamine, potassium carbonate, sodium hydride and the like. Solvent: dioxane, tetrahydrofuran, N, N-dimethylformamide, l-methyl-2-pyrrolidinone and the like. After the completion of the reaction, the proposed compound can be obtained, for example, by following the treatment; the reaction solution is poured into water, this is extracted with an organic solvent, and the organic layer is dried and concentrated. In addition, the resulting compound can also be purified by a method such as chromatography and the like. < Stage A9-3 > : Compound [19-4] can be produced by deprotection of compound [19-3], for example, in accordance with the method described in "Yuki Kagaku Jikken no Tebiki" vol. 4, (published by Kagaku Dojin), Protective Groups in Organic Synthesis (published by JOHN ILEY &SONS, INC.).
(Intermediary Production Method 10) [10 - 3] [10-4] V [wherein, R11, W and Z1 are the same as defined above, and R, 28 may represent chlorine or bromine, R 29 represents C_ to C6 alkyl such as methyl, ethyl and the like or phenyl, which can be substituted such as phenyl, 4-methylphenyl and the like, R30 represents C_ alkyl. to C6 such as methyl, ethyl and the like, or C to C6 haloalkyl, such as trifluoromethyl and the like, Y2 represents oxygen or sulfur, n represents 1 or 2].
(Intermediary Production Method 11) Compound [XXXXXI] can be produced, where X1 is nitro, fluorine, chlorine, bromine or iodine (compound [111-5]), by a method shown in the following scheme I 1 1 - 4] C l 1 1 - 5] [wherein, R3, R15, R25, Y, Q, and X2 are the same as defined above. R 32 represents C 1 -C 2 alkyl, which may be substituted such as methyl, ethyl, trifluoromethyl, trichloromethyl and the like, and R 33 represents nitro, fluoro, chloro, bromo or iodo].
(Intermediary Production Method 12) Compound [XXXI] can be produced by a method described in the following scheme.
Where Q, R1, R3, X1, X2 and Y are the same as defined above. < Process A12-l > : A process for producing compounds [1-12-1] from compound [XXXXXXI]. Compound [112-1] can be produced by reacting compound [XXXXXI] with compound [112-2] of formula [112-2] [I 1 2 - 2] wherein R1 is the same as defined above, and R31 represents Ci-alkyl to Ce / such as methyl, ethyl and the like. The reaction can be carried out without a solvent or in a solvent, and the reaction temperature is usually in the range of room temperature to 150 ° C or boiling point of the solvent. The amount of the compound [112-2] can be from 1 to 5 mole, based on 1 mole of the compound [XXXXXI]. Examples of the solvent to be used include aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin and the like, aromatic hydrocarbons such as toluene, xylene and the like. This reaction can be accelerated by using a dealcoholated agent such as molecular sieves 4A and 5A and the like.
After completion of the reaction, an object compound can be obtained by subjecting it to the ordinary treatment by the following procedure. 1) The reaction mixture is filtered and concentrated. 2) The reaction mixture is poured into water, and the deposited crystals are collected. 3) The reaction mixture is added to acids such as concentrated hydrochloric acid and the like or water, and this is extracted with an organic solvent and the resulting organic layer is washed with water, dried and concentrated. In addition, the subject compound can also be purified by a method such as chromatography, re-crystallization and the like. The compound [112-1] can exist as enol isomers and as the hydrate compound [112-3].
Where Q, R1, R3, X1, X2 and Y are the same as defined above, or mixtures thereof. < Process A12-2 > : A process to produce compound [XXXI] of compound [112-1]. Compound [XXXI] can be produced, for example, by reacting the compound [112-1] with cyanate in the presence of an acid. The reaction can be carried out without a solvent or in a solvent, and the reaction temperature is usually in the range of 55 to 150 ° C or boiling point of the solvent, preferably conducted in a range of room temperature to 50 ° C. , at the beginning, later, in a range of 55 to 150 ° C or boiling point of the solvent. The used cyanate includes potassium cyanate and sodium cyanate and the like. The acid used includes acetic acid, and the like. The amount of the cyanate used in this reaction is in a ratio of 1 to 10 mole, preferably 1 to 2 mole, based on 1 mole of the compound [112-1].
The amount of acids used in this reaction is in a ratio of 1 mole to a large excess amount based on 1 mole of the compound [112-1]. Examples of the solvent to be used include aliphatic hydrocarbons such as n-hexane, n-heptane and the like, aromatic hydrocarbons such as benzene, toluene, xylene and the like. After completion of the reaction, a target compound can be obtained, for example, by the following operation 1), 2) or 3). 1) The reaction solution is poured into water, this is extracted with an organic solvent, and the organic layer is dried and concentrated. 2) The reaction mixture is poured into water, and the precipitate is collected by filtration. 3) The reaction solution is concentrated as such, or, it is filtered if necessary, and the filtrate is concentrated. In addition, the subject compound can also be purified by a method such as chromatography, re-crystallization and the like. Compounds [XXI], [XXV], [XXVII], [XXXXX], [XXXXXIV] [XXXXXV], [19-1], [110-1] and [111-1] are commercially available, or may be produced by known methods. The present compounds have excellent activity as herbicides and some of them can exhibit excellent selectivity between crops and weeds. In other words, the present compounds have herbicidal activity against several weeds which can cause some alteration in the foliar treatment and the treatment in the soil in highland fields, as they are listed below: Onagráceas Weeds: Herb of the donkey that blooms large (Oenothera erythrosepala), cut leaf ass herb (Oenothera laciniata).
Ranunculáceas weeds: buttercup of hard seed (Ranunculus muricatus), hairy buttercup (Ranunculus sardous).
Polygonaceous weeds: wild buckwheat (Polygonum convolvulus), clear water pepper (Polygonum lapathifolium), water pepper pennsylvania (Polygonum pensylvanicum), peach tree (Polygonum persicaria), curly rosea (Rumez crispus), large leaf rosea (Rumex obtusifolius) , Japanese black centaurea (Polygonum cuspidatum).
Portuláceas weeds: Common purslane (Portulacea olerácea).
Cariofilaceous weeds: Common alsine (Stellaria media), sticky algae (Cerastium glomeratum).
Quenopodiaceous Weeds: Common Quelite: (Chenopodium albúm), kochia (Kochia scoparia).
Amaranth weeds: White chenopodium with red roots (Amaranthus retroflexus), soft white chenopodium (Amaranthus hybridus).
Cruciferous weeds (Brasiliaceae): wild radish (Raphanus raphanistrum), wild mustard (Sinapis arvensis), shepherd's purse (Capsella bursa-pastoris), pepper seed Virginia (Lepidiu virginicum).
Legume weeds (Fabáceas): Sesbania hemp (Sesbania exaltata), broom (Cassia obtusifolia), cuscuta Florida (Desmodium tortuosum), white clover (Trifolium repens), common vetch (Vicia sativa), black medicago (Medicago lupulina).
Malvaceae weeds: Alcotán (Abutilón theophrasti), spiny AIDS (Sida spinosa).
Violaceous weeds: Field thinking (Viola arvensis), wild thought (Viola tricolor).
Rubiaceous Weeds: Gallium (preseras) (Galium aparine! Convolvulaceous weeds: Leaf virgin mantle such as ivy (Ipomoea hederacea), mantle of the spiky virgin (Ipomoea purpurea), mantle of the virgin of whole leaves (Ipomoea herderacea var. Intergriscula), mantle of the chopped virgin (Ipomoea lacunosa), field vine (Convolvulus arvensis).
Labiaceous weeds: Red nettle (Lamium purpureum), leaf-stinging nettle (Lamium amplexicaule).
Solanaceous Weeds: Toloache (Datura stramonium), blackberry (Solanum nigrum).
Scrofulariaceae weeds: Veronica bird eye (Veronica persica), corn veronica (Veronica arvensis), shortleaf veronica (Veronica hederaefolia).
Composite weeds: Common Thistle (Xanthium pensylvanicum), common sunflower (Helianthus annuus), wild chamomile (Matricaria chamomilla), chamomile inolora (Matricaria perforata or odorata), marigold (Chrisanthemum segetum), pineapple-shaped weed (Matricaria matriacarioides), bitter common (Ambrosia artemisiifolia), giant bitter (Ambrosia trífida), erigeron del cañada (Erigenon canadiensis), Japanese sagebrush (Artemisia) -princeps), rod of St. Joseph high (Solidago altissima), common dandelion (Taraxacum officinale).
Boraginaceous weeds: Do not forget me (Myosotis arvensis).
Asclepidaceae weeds: Common milkweed (Asclepias syriaca).
Euphorbiaceous Weeds: Titímalo (Euphorbia helioscopia), titímalo with specks (Euphsrbia maculata).
Geraniaceas weeds: Geranium Carolina (Geranium carolinianum).
Oxalidáceas Weeds: Pink Acederilla (Oxalis corymbosa).
Cucurbitaceous weeds: Chayotillo espinoso (Sycios angulatus).
Gramineae weeds: Gracklefoot (Echinochloa crus-galli), green jopo (Setaria viridis) giant jopo (Setaria faberi), large crabgrass (Digitaria sanguinalis), southern garranchuelo (Digitaria ciliaris), goose grass (Eleusine indica), grass annual blue (Poa annual), black grass (Alopecurus myosuroides), wild oats (Avena fatua), Johnson grass (Sorghum halepense), grass grass (Agropyron repelens), velvety bromine (Bromus tectorum), bermuda grass (Cynodon dactylon), panicum marked or marked zacate (Panicum dichotomiflorum), Texas panicum (Panicum texanum), splintered cane (Sorghum vulgare), water jopo (Alopecurus geniculatus).
Commelinceous Weeds: Common Day Flower (Commelina communis) Echidna weeds: Field horsetail (Equisetum arvense) Cyperaceae weeds: Flat-edged rice (Cyperus iría), purple tulip (Cyperus rotundus), yellow tulip (Cyperus esculentus).
In addition, some of the present compounds do not exhibit significant phytotoxicity in the main crops such as corn (Zea maiz), wheat (Triticum aestivum), barley (Hordeum vulgare), rice (Oryza sativa), sorghum (Sorghum bicolor), soybean (Glicine max), cotton (Gossypium spp.), Beet (Beta vulgaris), peanut (Arachis hypogaea), sunflower (Helianthus annus), and cañola (Brasssica napus); horticultural crops such as ornamental plants, flowers, and vegetable crops. The present compounds may also attract effective control of several weeds which may cause some alteration in the cultivation of uncultivated soybeans (Glycine max), maize (Zea mays), wheat (Triticum aestivum), and other crops. In addition, some of the present compounds do not show significant phytotoxicity in the cultures. The present compounds also have herbicidal activity against several weeds, which may cause some alteration in flood treatment in raised fields, as listed below.
Gramineae Weeds: Farm or yard pasture (Echinocloa orzicola) Scrofulareceae weeds: Common false pimpernel (Lindernia procumbens) Litraceous weeds: Cup with Indian teeth (Rotalia indica) red stem (A mannia multiflora).
Elatinaceous Weeds: Aquatic plants (Elatine triandra).
Cyperaceae weeds: Sunflower-shaped sedge of small flower (Cyperus difformis), hard-stemmed junco (Scirpus juncoides), needle-shaped reed spike (Eleocharis acicularis), waterdrop (Cyperus serotinus), waterdrop ( Eleocharis kuroguwai).
Pontederiácea weeds: Monocoria (Monocoria vaginalis) Alismatácea weed: Arrowhead (Sagittaria pygmaea), arrowhead (Sagittaria trifolia), alisma (Alisma canaliculatum).
Potamogetonous weeds: round leaf pond weed iontamogeton distinctus).
Umbelliferae Weeds: Water species (Oenanthe javanicai In addition, some of the present compounds do not exhibit significant phytotoxicity in rice transplanted on high ground. The present compounds can also attract control of a wide variety of weeds, which are grown or will grow in the other uncultivated fields, in which the control of weeds in need such as boards, beds, side roads, back roads , green park fields, lands, parking lots, airports, industrial sites (eg factories, storage equipment), fallow fields, empty lots and the like, orchids, pasture fields, meadows, forests. The present compounds also have herbicidal activity against various aquatic weeds such as water hyacinth (Eichhornia crassipes), which are growing or growing on the banks of rivers such as creeks, channels, waterways or reservoirs. The present compounds have substantially the same characteristics as those of the herbicidal compounds described in the published specification of International Patent Application No. W095 / 34659. In the case where crops are cultivated with tolerance imparted by the introduction of a gene with tolerance to the herbicide described in the published specification, the present compounds can be used at larger proportions than those used when ordinary crops without tolerance are grown, which makes it possible to control other unfavorable weeds more effectively. When the present compounds are used as the active ingredients of herbicides, they are usually mixed with solid or liquid carriers or diluents, surfactants and other auxiliary agents to give emulsifiable, wettable concentrates, powders, flowables, granules, concentrated emulsions, water dispersible granules or other formulations These formulations may contain some of the present compounds as an active ingredient in an amount of 0.001 to 80% by weight, preferably 0.005 to 70% by weight, based on the total weight of the formulation. The solid carrier may include fine powders of mineral materials such as kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, and calcite.; fine powders of organic substances such as walnut shell powder; fine powders of organic substances soluble in water such as urea; fine powders of inorganic salts such as ammonium sulfate; and fine powders of synthetic hydrated silicon oxide. The liquid carrier may include aromatic hydrocarbons such as methylnaphthalene, phenylethylethane, and alkylbenzene (eg, xylene); alcohols such as isopropanol, ethylene glycol and 2-ethoxyethanol; esters such as dialkyl esters of phthalic acid; ketones such as acetone, cyclohexanone and isophorone; mineral oils such as machine oil; vegetable oils such as soybean oil and cottonseed oil; dimethyl sulfoxide, N, N-dimethylformamide, acetonitrile, N-methylpyrrolidone, water and the like. The surfactant used for emulsification, dispersion or spreading may include anionic type surfactants, such as alkylsulfates, alkylsulfonates, alkylarylsulfonates, dialkylsulfosuccinates, and polyoxyethylene alkylaryl ether phosphates; and surfactants of the anionic type, such as alkyl polyoxyethylene ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene polyoxypropylene block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. The other auxiliary agent may include lignin sulfonates, alginates, polyvinyl alcohol, gum arabic, CMC (carboxymethylcellulose) and PAP (isopropyl acid phosphates). The present compounds are usually formulated and then used for soil, foliar or flood treatment in the pre- or postemergence of weeds. Soil treatment may include treatment of the soil surface and incorporation into the soil. The treatment to the ground can include the application on the plants and directed application in which, a chemical is only applied to the weeds, in this way the plants of cultures are kept free. The present compounds can often have increased herbicidal activity when used in admixture with other herbicides. They can also be used in mixtures with insecticides, acaricides, nematocides, fungicides, bactericides, plant growth regulators, fertilizers, and soil conditioners. Shown below are such herbicides. Atrazine, cyanazine, dimethamethrin, metribuzine, promethene, simazine, symmetry, chlorotoluron, diuron, fluometuron, isoproturon, linuron, metabenzthiazuron, propanil, bentazone, bromoxynil, ioxinil, pyridate, butamiphos, dithiopyrim, etalfluralin, pendimethalin, thiazopyrim, trifluralin, acetochlor, alachlor, butachlor, dietyl-ethyl, dimethenamid, flutiamide, mefenacet, metolachlor, pretilachlor, prpaclor, cinmetilin, acifluorfen, acifluorfen-sodium, benzfendizone, bifenox, butafenacil, clometoxinil, fomesafen, lactofen, oxadiazone, oxadiargyl, oxyfluorfen, carfentrazone-ethyl, fluazolato, flumicloracpentilo, flumioxazina, flutiacet-methyl, isopropazol, sulfentrazona, thidiazimina, azafenidina, piraflufen-etil, cinidon-etil, difenzocuat, dicuat, paraquat, 2,4-D, 2,4-DB, clopiralid, dicamba, fluroxipiro, MCPA, MCPB, mecoprop, quinolorac, triclopyr, azimsulfuron, bensul furonmethyl, chlorimuron-ethyl, chlorsulfuron, cloransulam-methyl, cyclosulfauron, diclosulam, ethoxysulfuron, fl azasulfuron, flucarbazone, flumetsulam, flupirsulfuron, halosulfuron-methyl, imazosulfuron, indosulfuron, metosulam, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron-methyl, procarbazon-sodium, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfameturon-methyl, sulfosulfuron, triasulfuron, tribenuron-methyl, tritosulfuron, tifensul furon-methyl, triflusulfuron-methyl, pyribenzoxime, bispyribac-sodium, piriminobac-methyl, piritiobac-sodium, imazamet, imazametabenz-methyl, imazamox, imazapic, imazapir, imazaquin, imazetapir, tetraloxidim, alloxydim-sodium clethodim, clodinafop-propargyl, cyhalofop-butyl, diclofob-methyl, fenoxapropethyl, fenoxaprop-p-ethyl, fluazifop-butyl, fluazifop-p-butyl, haloxy fop-methyl, quizalofop-p-ethyl, sethoxydim, trialcoxydim, Diflufenican, flurtamone, norflurazone, benzophenap, isoxaflutola, pirazolato, pirazoxifeno, sulcotriona, clomazona, mesotrione, isoxaclortola, Bialafos, glufosinate-ammonium, glyphosate, sulfosate, diclobenil, isoxabe no, benthiccarb, butylate, dimepiperate, EPTC, esprocarb, molinate, puributicarb, trialate, diflufenzopyr, bromobutido, DMSA, MSMA, cafenstrol, daimron, epoprodane, flupoxam, methobenzuron, pentoxazone, piperofos, triaziflam, Beflubutamid, benzobiciclon, clomeprop, fentrazamide, flufenacet, florasulam, indanofan, isoxadifen, mesotrione, naploanilido, oxaziclomefona, petoxiamida, fnotiol, piridafol. The above compounds are described in the Fram Chemicals Handbook, 1995 (Meister Publishing Company); AG CHEM NEW COMPOUND REVIEW, VOL. 13, 1995, VOL. 15, 1997, VOL. 16, 1998 or, VOL. 17, 1999 (AG CHEM INFORMATION SERVICES) 0 Josouzai Kenkyu Souran (Hakuyu-sha). When the present compounds are used as the active ingredients or herbicides, the application amount although may vary with the weather conditions, formulation types, application times, application methods, soil conditions, crops to be protected, and weeds a to be controlled, is usually within the range of 0.01 to 20,000 g, preferably, 1 to 12,000 g per hectare. In the case of emulsifiable concentratesWettable powders, flowable emulsions, concentrated emulsions, water dispersible granules, or the like, are usually applied after diluting them in their prescribed amounts with water (if necessary, containing an adjuvant such as a spreading agent) at a rate of 10%. up to 1000 liters per hectare. In the case of granules of some types of flowables, they are usually applied as such without any dilution. The adjuvant which may be used, if necessary, may include, in addition to the surfactant described above, polyoxyethylene resin acids (esters), lignin sulfonates, abietates, dinaphthylmethane disulfonates, crop oil concentrates, and vegetable oils such as oils. of soybeans, corn oil, cottonseed oil, and sunflower oil.
(Examples) The following production examples, formulation examples and test examples and the like, will be further illustrated in the present invention in detail below, but do not limit the scope of the present invention. First, the production examples and the intermediary production examples of the present compounds are shown. The compound numbers of the present compounds are described in the following Tables 1 to 10.
Production Example 1: Production of the present compound 1-12 109 mg of 2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenol and 70 mg of 2 -chloro-5- [1- (methoxycarbonyl) ethoxy] pyrimidine were dissolved in 1.0 ml of dimethyl sulfoxide, to this solution were added 10 mg of copper bromide (I) and 12 mg of anhydrous lithium carbonate, and the mixture it was stirred for 2 hours at 120 ° C. The reaction solution was cooled to room temperature, then, this reaction solution was poured into ice water, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 10 mg of 2- ([2- {2-chloro-4-fluoro-5- [3-methyl-2-, 6-dioxo-4- ( methyl trifluoromethyl) -1, 2, 3, 6-tetrahydropyrimidin-1-yl] phenoxy] pyrimidin-5-yl] oxy) propionate (compound present 1-12). XH NMR (CDC1./300 MHz) d (ppm): 1.65 (d, 3H), J = 7.0 Hz), 3.56 (s, 3H), 3.78 (s, 3H), 4.72 (q, 1H, J = 7.0 Hz), 6.36 (s, 1H), 7.21 (d, 1H, J = 6.8 Hz), 7.39 (d, 1H, J = 8.7 Hz), 8.20 (s, 2H) Production Example of Intermediary 1: The production of 2-Chloro-5- [1- (methoxycarbonyl) ethoxy] pyrimidine is used in the production of Example 1 A mixture of 0.17 g of 2-chloro-5-hydroxypyrimidine, 0.22 g of methyl 2-bromopropionate, 0.20 g of anhydrous potassium carbonate and 2.6 ml of N, N-dimethylformamide was stirred at 60 ° C for 1 hour. The reaction solution was cooled to room temperature, then, poured into water, and extracted with t-butylcyomethyl ether. The organic layer was dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.17 g of 2-chloro-5- [1- (methoxy carbonyl) ethoxy] oirimidine. ? E NMR (CDCl3 / 300 MHz) d (ppm): 1.68 (d, 3H, J = 6.6Hz), 3.79 (s, 3H), 4.82 (q, 1H, J = 6.7 Hz), 8.27 (s, 2H) ) Production Example 2: Production of the present compound 7-125 A mixture of 0.30 g of 3- [2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy } -2- (methoxycarbonyl) methoxypyridine (compound present 7-7), 0.06 g of sodium carbonate and 3.0 ml of c-pentanol was stirred for 1.5 hours at 100 ° C, then 2 hours at 120 ° C. The reaction solution was cooled to room temperature, then, poured into water, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was chromatographed on silica gel to obtain 0.15 g of 3- (2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1, 2, 3 , 6-tetrahydropyrimidin-1-yl] phenoxy] -2- (c-pentyloxycarbonyl) methoxypyridine [compound present 7-125]. XH NMR (CDCl3 / 300 MHz) d (ppm): 1.5-1.9 (m, 8H ), 3.50 (q, 3H, J = 1.1 Hz), 4.7-5.0 (m, 2H), 5.1-5.2 (m, 1H), 6.29 (s, 1H), 6.91 (dd, 1H, J = 7.8, 4.9 Hz), 6.94 (d, 1H J = 6.5 Hz), 7.30 (dd, 1H, J = 7.8, 1.6 Hz), 7.37 (d, 1H, J = 8.9 Hz), 7.91 (dd, 1H, J = 4.9, 1.6 Hz) Production Example 3: Production of the present compound 1-2 339 mg of 2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethoxy) -l, 2,3,6-terahydropyrimidin-1-yl] phenol and 217 mg were dissolved of 2-chloro-4- [1- (methoxycarbonyl) ethoxy] pyrimidine in 2 ml of N, N-dimethylformamide, to this solution was added 150 mg of potassium carbonate, and the mixture was stirred for 2 hours at 80 ° C . The reaction solution was cooled to room temperature, thenThis reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 256 mg of 2- ([2- {2-chloro-4-fluoro-5- [3-methyl-2-6-dioxo-4- ( methyl trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy] pyrimidin-4-yl] oxy) propionate [compound present 1-2]. X H NMR (CDCl 3/300 MHz) d (ppm): 1.56 (d, 3 H, J = 7.1 Hz), 3.55 (s, 3 H), 3.69 (s, 3 H), 5.32 (q, 1 H, J = 6.3 Hz) , 6.35 (s, 1H), 6.59 (d, 1H, J = 5.6 Hz), 7.18 (d, 1H, J = 6.1 Hz), 7.39 (d, 1H, J = 9.1 Hz), 8.28 (d, 1H, J = 5.7 Hz).
Production Example 4: Production of the present compound 3-2 156 mg 2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenol and 100 mg of sodium were dissolved. 4-chloro-2- [1- (methoxycarbonyl) ethoxy] pyrimidine in 1 ml of N, N-dimethylformamide, to this solution was added 75 mg of potassium carbonate, and the mixture was stirred for 2 hours at room temperature. The reaction solution was poured into ice water, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate. The residue was subjected to silica gel column chromatography to obtain 69 mg of 2- ([4. {2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- ( trifluoromethoxy) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy] pyrimidin-2-yl] oxy) propionate [compound present 3-2]. 1 H NMR (CDCl 3/300 MHz) d (ppm): 1.56 (d, 3 H), J = 7.1 Hz), 3.55 (s, 3 H), 3.65 (s, 3 H), 5.0-5.3 (m, 1 H), 6.35 (s, 1H), 6.63 (d, 1H), J = 5.8 Hz), 7.20 (d, 1H, J = 6.4 Hz), 7.39 (d, 1H, J = 8.6 Hz), 8.38 (d, 1H, J = 5.8 Hz).
Production Example of Intermediate 2: The production of 2-chloro-4- [1- (methoxycarbonyl) ethoxy] pyrimidine and 4-chloro-2- [1- (methoxycarbonyl) ethoxy] pyrimidine was used in the Production of Examples 3 and 4 A mixture of 3.12 g of methyl lactate and 10 ml of acetonitrile was added to the mixture of 1.2 g of sodium hydride and 40 ml of acetonitrile by dropping under cooling on ice, and the mixture was stirred for 30 minutes. To this was added a mixture of 4.47 g of 2,4-dichloropyrimidine and 10 ml of acetinitrile by dropping at the same temperature, and the mixture was stirred at 60 ° C for 2 hours. This reaction solution was cooled to room temperature, then, poured into water, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 2.5 g of 2-chloro-4- [1- (methoxycarbonyl) ethoxy] pyrimidine and 0.25 g of 4-chloro-2- [1- (methoxycarbonyl) ethoxy] pyrimidine. 2-Chloro-4- [1- (methoxycarbonyl) ethoxy] pyrimidine.
R NMR (CDCl3 / 250 MHz) d (ppm): 3.51 (q, 3H, J = 1.2 Hz), 5.04 (s, 2H), 6.31 (s, 1H), 6.87 (d, 1H, J = 5.9 Hz) , 6.9-7.1 (m, 4H), 7.3-7.5 (m, 5H), 7.84 (d, 1H, J = 8.6 Hz). 4-chloro-2- [1- (methoxycarbonyl) ethoxy] pyrimidine. X H NMR (CDCl 3/250 MHz) d (ppm): 1.67 (d, 3 H, J = 7.0 Hz), 3.75 (s, 3 H), 5.33 (q, 1 H, J = 7.0 Hz), 7.03 (d, 1 H, J = 5.3 Hz), 8.38 (d, 1H, J = 5.3 Hz).
Production Example 5: Production of the present compound 7-7 First Stage: 2.08 g of potassium carbonate was added to a solution of 3.0 g of 3-hydroxy-2- (methoxycarbonyl) methoxypyrimidine and 2.95 g of N- (2,5-diluoro-4-nitrophenyl) acetamide in 40 ml of N, N-dimethylformamide. The mixture was stirred for 2 hours at a temperature of 60 to 70 ° C. Then, the mixture was cooled to room temperature, poured into water, extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over magnesium sulfate, and concentrated to obtain crude crystal. The crude was washed with diisopropyl ether to obtain 3.67 g of N- [2-fluoro-5-. { 2- (methoxycarbonyl) methoxy-3-pyridyloxy} -4-nitrophenyl] acetamide. 1R NMR (CDC1./250 MHz) d (ppm): 2.21 (s, 3H), 3.72 (s, 3H), 4.90 (s, 2H), 6.96 (dd, 1H, J = 7.8, 5.0 Hz), 7.35 (dd, 1H, J = 7.8, 1.6 Hz), 7.5-7.6 (b, 1H), 7.90 (d, 1H), J = 10.6 Hz), 7.97 (dd, 1H), J = 5.0, 1.6 Hz), 8.15 (d, 1H, J = 6.8 Hz).
The following compounds were prepared in a similar manner: N- [2-fluoro-5-. { 2- (Ethoxycarbonyl) ethoxy-3-pyridyloxy} -4-nitrophenyl] acetamide. N- (2-fluoro-5- [2- ({1- (methoxycarbonyl) ethoxy] - 3-pyridyloxy] -4-nitro phenyl) acetamide. N- (2-fluoro-5- [2- ({1- (ethoxycarbonyl) ethoxy} - 3-pyridyloxy] -4-nitrophenyl) acetamide.
Second Stage To a mixture of 3.6 g of iron powder, 10 ml of acetic acid and 1 ml of water was added to a solution of 3.67 g of N- [2-fluoro-5- (2-methoxycarbonyl) methoxy-3-pyridyloxy } -4-nitrophenyl] acetamide in 12 ml of acetic acid and 2 ml of ethyl acetate, by dripping while kept at the temperature of the reaction solution at 45 ° C or lower. After the reaction was complete, the mixture was stirred for 1 hour at 40 ° C, then, the reaction mixture was filtered through celite, and concentrated. The residue was diluted with a solution of aqueous sodium bicarbonate, and extracted with ethyl acetate. The organic layer was washed with a solution of aqueous sodium bicarbonate, dried over anhydrous magnesium sulfate, and concentrated. Then, the resulting residue was washed with diisopropyl ether to obtain 3.09 g of N- [4-amino-2-fluoro-5-. { 2- (methoxycarbonyl) methoxy-3-pyridi loxi} phenyl] acetamide.
? E NMR (CDCl3 / 250 MHz) 6 (ppm): 2.15 (s, 3H), 3.77 (s, 3H), 3.9-4.1 (b, 2H), 5.03 (s, 2H), 6.56 (d, 1H, J = 11.8 Hz), 6.84 (dd, 1H, J = 7.9, 5.0 Hz), 7.0-7.2 (b, 1H), 7.14 (dd, 1H, J = 7.9, 1.5 Hz), 7.80 (dd, 1H, J = 5.0, 1.5 Hz), 7.84 (d.1H, J = 7.6 Hz). The following compounds were prepared in a similar manner N- [4-amino-2-fluoro-5-. { 2- (Ethoxycarbonyl) ethoxy-3-pyridyloxy} phenyl] acetamide. N- (4-amino-2-fluoro-5- [2- ({1- (methoxycarbonyl) ethoxy} - 3-pyridyloxy] phenyl) acetamide.
N- (4-amino-2-fluoro-5- [2- ({1- (ethoxycarbonyl) ethoxy} - 3-pyridyloxy] phenyl) acetamide.
Third Stage: A solution of 2.01 g of isoamyl nitrite in 1 ml of acetonitrile was added to a mixture of 2.0 g of N- [4-amino-2-fluoro-5-. { 2- (methoxycarbonyl) methoxy-3-pyridyloxy} phenyl] acetamide, 1.13 g of copper (I) chloride, 2.31 g of copper (II) chloride and 20 ml of acetonitrile per drop at room temperature, and the mixture was stirred for 1 hour. This reaction solution was poured into 2% hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 1.04 g of N- [4-chloro-2-fluoro-5-. { 2- (methoxycarbonyl) methoxy-3-pyridyloxy} phenyl] acetamide.
X H NMR (CDCl 3/250 MHz) d (ppm): 2.18 (m, 3 H), 3.75 (s, 3 H), 4.98 (s, 2 H), 6.87 (dd, 1 H, J = 8.4, 9 Hz), 7.08 ( dd, 1H, J = 7.8, 1.4 Hz), 7.23 (d, 1H), J = 10.3 Hz), 7.3-7.4 (b, 1H), 7.86 (dd, 1H, J = 4.9, 1.4 Hz), 8.07 ( d, 1H), J = 7.3 Hz).
The following compounds were prepared in a similar manner N- [4-chloro-2-fluoro-5-. { 2- (Ethoxycarbonyl) ethoxy-3-pyridyloxy} phenyl] acetamide. N- (4-chloro-2-fluoro-5- [2-. {L- (methoxycarbonyl) ethoxy.} - 3-pyridyloxy] phenyl) acetamide. N- (4-chloro-2-fluoro-5- [2-. {L- (ethoxycarbonyl) ethoxy.} - 3-pyridyloxy] phenyl) acetamide.
Fourth Step A mixture of 20 ml of a methanol solution of borontrifluoro methanol complex and 1.04 g of N- [4-chloro-2-fluoro-5-. { 2- (methoxycarbonyl) methoxy-3-pyridyl lox i} phenyl] acetamide was stirred for 3 hours at a temperature of 60 to 70 ° C. Subsequently, the reaction solution was concentrated, the residue was diluted with a solution of aqueous sodium bicarbonate, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over magnesium sulfate, and concentrated, and the resulting residue was purified by column chromatography, concentrated to obtain 0.87 g of 4-chloro-2-fluoro-5-. { 2- (methoxycarbonyl) methoxy-3-pyridyloxy} aniline. 2 H NMR (CDCl 3/250 MHz) d (ppm): 3.77 (s, 3 H), 3.7-3.9 (b, 2 H), 5.00 (s, 2 H), 6.49 (d, 1 H, J = 8.2 Hz), 6.88 ( dd, 1H, J = 7.9, 5.0 Hz), 7.08 (d, 1H, J = 10.3 Hz), 7.10 (dd, 1H, J = 7.9, 1.6 Hz), 7.87 (dd, 1H, J = 5.0, 1.6 Hz ).
The following compounds were prepared in a similar manner 4-chloro-2-fluoro-5-. { 2- (Ethoxycarbonyl) methoxy-3-pyridyloxy} aniline. 4-chloro-2-fluoro-5- [2-. { 1- (methoxycarbonyl) ethoxy} -3-pyridyloxy] aniline. 4-chloro-2-fluoro-5- [2-. { 1- (ethoxycarbonyl) ethoxy} -3-pyridyloxy] aniline.
Fifth Stage: A mixture of 0.50 g of 4-chloro-2-fluoro-5-. { 2- (methoxycarbonyl) methoxy-3-pyridi loxy) aniline, 0.28 g of ethyl trifluoroacetate and 10 ml of toluene was subjected to azeopyping reaction with ethanol removal to pass through 5a molecular sieves for 3 hours. After cooling, the reaction solution was concentrated to obtain 0.71 g of N- [4-chloro-2-fluoro-5-. { 2- (methoxycarbonyl) methoxy-3-pyridyloxy} phenyl] trifluoroacetoacetamide. Melting point: 158.8 ° C Sixth Stage: To a mixture of 0.71 g of N- [4-chloro-2-fluoro-5-. { 2- (methoxycarbonyl) methoxy-3-pyridyloxy} phenyl] trifluoroacetoacetamide and 2 ml of acetic acid, 0.33 g of potassium cyanate was added, and the mixture was stirred at 50 ° C for 1 hour, then, at 110 ° C for 1.5 hours. After cooling, water was added to the reaction mixture and the mixture was extracted with ethyl acetate. The organic layer was washed with a solution of aqueous sodium bicarbonate, and saturated saline, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 0.30 g of 3- (2-chloro-4-fluoro-5- [2,6-dioxo-4- (trifluoromethyl) -1, 2, 3, 6 -tetrahydropyrimidin-1-yl] phenoxy] -2- (methoxycarbonyl) methoxypyridine.
X H NMR (CDCl 3/250 MHz) d (ppm): 3.70 (s, 3 H), 4.93 (s, 2/2 H), 4.94 (s, 2/2 H), 6.19 (s, 1 H), 6.9-7.0 (m , 2H) 7.3-7.4 (m, 1H), 7.38 (d, 1H, J = 8.9 Hz (7.93 (dd, 1H, J = 4.9, 1.6 Hz). Point, melting: 75.3 ° C Seventh Stage: To a mixture of 0.10 g of 3-. { 2-Chloro-4-fluoro-5- [2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (methoxycarbonyl) methoxypyridine, 1 ml of acetonitrile and 31 mg of potassium carbonate, 32 mg of potassium iodide was added to the mixture, and the mixture was stirred at room temperature for 1.5 hours. 64 mg of methyl iodide was added to the mixture, and the mixture was stirred at 50 ° C for 1 hour. The mixture was filtered, and the filtrate was concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 97 mg of 3- (2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2 , 3,6-tetrahydropyrimidin-1-yl] phenoxy] -2- (methoxycarbonyl) methoxypyridine [compound present 7-7].
Production Example 6: Production of compound 3-12 present 338 mg of 2-nd r o- 4 -f luoro- 5 - [3-methyl-1, 2, 6-dioxo-4- (trifluoromethyl) -1, 2, 3, 6-tetr ahydropyrimidin- 1 -i 1 ] f enol and 216 mg of 4-chloro-6- [1- (methoxycarbonyl) ethoxy] pyrimidine were dissolved in 2 ml of N, N-dimethylfuran, to this solution were added 150 mg of potassium carbonate, and The mixture was stirred for 2 hours at 60 ° C. The reaction solution was cooled to room temperature, then, this reaction solution was poured into ice water, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 101 mg of 2- ([4- (2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2, 3, 6 -t et rah id opi r imidi n-1-yl] phenoxy) pyrimidin-6-yl] oxy) methyl propionate [compound 3-12 present]. X H NMR (CDCl 3 / 3OO MHz) d (ppm): 1.62 (d, 3 H), J = 7.0 Hz), 3.56 (s, 3 H), 3.75 (s, 3 H), 5.41 (q, 1 Hz, J = 7, 0 H), 6.36 (s, 1H), 6.37 (s, 1H), 7.17 (d, 1H, J = 6.5 Hz), 7.40 (d, 1H), J = 9.1 Hz), 8.34 (s, 1H).
Production Example 7: Production of compound 5-17 present To a solution of 0.21 g of 4-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -3-Hydroxy-5-me t-ilpy-zol in 1.0 ml of, N-dimethyl-1-formamide 0.10 g of methyl bromoacetate and 0.20 g of potassium carbonate were added, and the mixture was stirred for 3 hours at room temperature. The dilute hydrochloric acid was poured into this reaction solution, and extracted with ethyl acetate. The organic layer was washed with saturated saline solution, dried over anhydrous magnesium sulfate. This solution was subjected to silica gel column chromatography to obtain 0.06 g of 3- (methoxycarbonyl) methoxy-4-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -5-methylpyrazole [compound 5-17 present].
X H NMR (CDCl 3/300 MHz) d (ppm): 2.16 (s, 3H) 3.51 3H) 3.69 (s 3H '4.77 (s, 2H), 6. 30 (s, 1H), 7.12 (d, 1H, J = 6.5 Hz), 7.31 (d, 1H, J = 9.0 Hz) Production Example 8: Production of the optical R-isomer of compound 5-12 present To a solution of 0.13 g of 4-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-y1] f enoxy} - 3-Hydr oxy-5-met i Ipi ra zo 1 in 2.0 ml of ethyl acetate were added 0.10 g of (S) - (-) -methyl lactate or, 0.26 g of triphenylphosphine and 0.5 ml of a 40% solution of diisopropyl azodicarboxylate in toluene, and the mixture was stirred for 3 hours at room temperature. 6 ml of n-hexane were poured into this reaction solution, and the precipitated insoluble substance was removed by filtration. This solution was subjected to silica gel column chromatography to obtain 0.09 g of (R) -3-. { 1- (methoxycarbonyl) ethoxy} -4- . { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1, 2, 3, 6-tetrahydropyrimidin-1-yl] phenoxy] -5- methylpyrazole [optical isomer R of compound 5-12 present, described below, represented as 5, -12-R]. "2 H-NMR (CDC1./300 MHz) d (ppm): 1.51 (m, 3H), 2.15 ( s, 3H), 3.48 (s, 3 / 2H), 3.52 (s, 3 / 2H), 3.67 (s, 3H), 5.05 (m, 1H), 6.30 (s, 1 / 2H), 6.31 (s, 1 / 2H), 7.13 (d, 1 / 2H), J = 6.5 Hz), 7.18 (s, 1 / 2H, J = 6.6 Hz), 7.31 (d, 1H, J = 8.7 Hz) [a] D + 16.4 ° (c? .5 methanol) Production Example 9: Production of the optical S-isomer of compound 5-12 present To a solution of 0.13 g of 4-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} - 3-Hydroxy-5-me t-ilpy-zol in 2.0 ml of ethyl acetate 0.10 g of (R) - (+) - methyl γ lactate, 0.26 g of triphenylphosphine and 0.5 ml of a 40% solution were added. % diisopropyl azodicarboxylate in toluene, and the mixture was stirred for 3 hours at room temperature. 6 ml of n-hexane were poured into this reaction solution, and the precipitated insoluble substance was removed by filtration. This solution was subjected to silica gel column chromatography to obtain 0.08 g of (S) -3-. { 1- (methoxycarbonyl) ethoxy} -4-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -l, 2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -5-methylpyrazole [optical isomer S of compound 5-12 present, described below, represented as 5-12-S]. XH-NMR (CDC1./300 MHz) d (ppm): 1.51 (m, 3H), 2.15 (s, 3H), 3.49 (s, 3 / 2H), 3.52 (s, 3 / 2H), 3.67 (s) , 3H), 5.05 (m, 1H), 6.30 (s, 1 / 2H), 6.31 (s, 1 / 2H), 7.13 (d, 1 / 2H, J = 6.8 Hz), 7.18 (d, 1 / 2H) , J = 6.5 Hz), 7.31 (d, 1H, J = 8.8 Hz) [] D - 16.0 ° (c? .5 methanol) Production Example 3 of the Intermediary: Production of the 4 -. { 2-cl or o -4-f luoro-5 - [3 -me t i 1 -2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -3-hydroxy-5-methylpyrazole used in Production Examples 7 to 9.
Step One: 10.0 g of 2-chloro-4-fluoro-5 - [3-met il-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenol dissolved in 30 ml of N, -dimet i 1 formamide, to this was added 5.0 ml of triethylamine, then 5.0 g of methyl 2-chloroacet oacetate were added to the resulting mixture at room temperature with stirring. Then, the agitation was continued for 10 minutes at room temperature and for 1 hour at 60 ° C. 2.0 ml of triethylamine and 2.0 g of 2-chloroacetoacetat or methyl were added to this solution, then the mixture was further stirred for 1 hour at 60 ° C. The reaction solution was stirred overnight at room temperature, then, the reaction solution was poured into water with ice and dilute hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 7.86 g of 2 -. { 2-chloro-4-f luoro-5 - [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-> tetrahydropyrimidin-1-yl] phenoxy} -3-oxobut metíl time.
XH-NMR (CDCl3 / 300 MHz) d (ppm): 2.01 (s, 3 / 2H), 2.47 (s, 3 / 2H), 3.55 (s, 3H), 3.75 (s, 3 / 2H), 3.81 (s, 3 / 2H), 4.99 (s, 1 / 2H), 6.34 (s, 1 / 2H), 6.35 (s, 1 / 2H), 6.65 (d, 1 / 2H, J = 6.4 Hz), 6.83 (m, 1 / 2H), 7.35 (m, 1H) Step Two 3. 09 g of 2 -. { 2-chloro-4-fluoro-o-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} Methyl-3-oxobutyrate and 1.23 g of methyl carbazate were suspended in 30 ml of toluene, and the mixture was heated under reflux for 5 hours. The solution was cooled to room temperature, then, the reaction solution was poured into ice water and dilute hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was washed with a mixed solvent of n-hexane: ethyl acetate (3: 1) to obtain 2.94 g of 4 -. { 2-Chloro-4-fluoro-5- [3-methyl-2, 6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -3-hydroxy-5-methylpyrazole. 1H-NMR (CDC1. + CD.OD / 250 MHz) d (ppm): 2.08 (s, 3H), 3.51 (s, 3H), 6.32 (s, 1H), 6.81 (d, 1H, J = 6.5 Hz ), 7.32 (d, 1H, J = 8.8 Hz) Production Example 10: Production of compound 6-2 present 0. 40 g of 2-chloro-4-fluoro-5- (3-methyl) -2,6-dioxo-4- (trifluoromethyl) -1, 2, 3, 6-tet rahydropyr imidin-1-yl] phenyl mercaptan were dissolved in 6 ml of acetonitrile, 0.31 g of potassium carbonate was added to this solution, and the mixture was stirred for 30 minutes, then 0.29 g of 2-chloro-4 - [1 - (methoxycarbonyl) ethoxy] pyridine were added and the mixture was stirred for 3 hours. This reaction solution was poured into ice water, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.46 g of 2- ([2- {2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- ( trifluoromethyl) -1, 2, 3, 6-tetrahydropyrimidin-1-yl] phenylthio, pyrimidin-4-yl] oxy} methyl propionate [compound 6-2 present]. 1 H-NMR (CDCl 3/300 MHz ) d (ppm): 1.49 (d, 3H, J = 7.1 Hz), 3.56 (d, 3H, J = 1.1 Hz), 3.67 (d, 3H, J = 1.3 Hz), 5.23 (m, 1H), 6.36 (s, 1H), 6. 52 (d, 1H, J = 5.7 Hz), 7.46 (d, 1H, J = 9.2 Hz), 7.62 (m, 1H), 8.26 (d, 1H, J = 5.7 Hz) melting point: 60.2 ° C Production Example 4 of the Intermediary: Production of 2-chloro-4-f luoro-5 - [3-methyl-1, 2,6-dioxo-4- (trifluoromethyl) -1, 2, 3, 6-te trahidropi rimidin - 1-yl] phenyl mercaptan used in Production Example 10 1. 65 g of 2-chloro-4-fluoro-5 - [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] benzenesulfonyl chloride were dissolved in 16 ml of acetic acid, to this was added 4.4 g of zinc, then, it was reacted while heating under reflux. After completion of the reaction, the reaction solution was cooled, then poured into ice water, extracted with ethyl acetate, and filtered. The filtrate was separated, then the organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated to obtain 1.35 g of 2-chloro-4-fluoro-5- [3-me t -2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenyl mercaptan. XH-NMR (CDC1./300 MHz) d (ppm): 3.55 (m, 3H), 3.86 (s, 1H), 6.36 (s, 1H), 7.27 (d, 1H, J = 6.4 Hz), 7.33 ( d, 1H, J = 9.1 Hz) melting point: 132.5 ° C Production Example 11: Production of compound 2-2 present 200 mg of 2 -. { 2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} - 3-Hydroxypyridine and 80 mg of methyl 2-bromopropionate were dissolved in acetonitrile, to this were added 66 mg of potassium carbonate, and the mixture was stirred for hours at 60 ° C. This reaction solution was poured into ice water , and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 77 mg of 2-. { 2-Chloro-4-f-luoro-5- [3-met il-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -3- . { 1- (methoxycarbonyl) ethoxy} pyridine [compound 2-2 present]. XH-NMR (CDCl3 / 250 MHz) d (ppm): 1.67 (d, 3H, J = 6.8 Hz), 3.55 (m, 3H), 3.76 (s, 3H), 4.94 (q, 1H, J = 6.9 Hz ), 6.35 (s, 1H), 6.95 (m, 1H), 7.20 (d, 1H, J = 6.8 Hz), 7.28 (m, 1H), 7.39 (d, 1H, J = 9.0 Hz), 7.75 (m , 1 HOUR ) Production Example 12 Production of compound 2-7 present 60 mg of 2 -. { 2-chloro-4-fluoro-5 - [3-methyl-2, 6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} 3-hydroxypyridine and 20 mg of methyl bromoacetate were dissolved in 2 ml of acetonitrile, to this was added 20 mg of potassium carbonate, and the mixture was stirred for 2 hours at 60 ° C. This reaction solution was poured into ice water, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 60 mg of 2 -. { 2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -3- (methoxycarbonyl 1) methoxypyridine [compound 2-7 present]. ^ -NMR (CDC1./300 MHz) d (ppm): 3.55 (s, 3H), 3.80 (s, 3H), 4.81 (s, 2H), 6.35 (s, 1H), 6.97 (m, 1H), 7.21 (d, 1H, J = 6.8 Hz), 7.27 (m, 1H), 7.39 (d, 1H, J = 9.1 Hz), 7.75 (d, 1H, J = 4.1 Hz) Production Example 5 of the Intermediary: Production of 2-. { 2-chloro-4-f luoro-5 - [3-methyl-2, 6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} - 3-Hydroxypyridine used in Production Examples 11 and 12 Step Prime ro: 11.8 g of 2-chloro-4-fluoro-5- [3-met il-2, β-dioxo-4- (trifluoromethyl) -1, 2, 3, 6-tetrahydropyrimidin-1-yl] Phenol and 5.2 g of 2-chloro-3-nor tropiridine were dissolved in 10 ml of toluene, to this were added 2.3 g of potassium hydroxide and 5 μg of 18-crown-β, and the mixture was stirred for 3 hours at 90 ° C. The reaction solution was cooled to room temperature, then, the solvent was distilled off, and the residue was poured into ice water, and the precipitated crystals were collected by filtration to obtain 11.5 g of 2-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -3-nitropyridine. ^ -H-NMR (CDCl3 / 250 MHz) d (ppm): 3.56 (m, 3H), 6.36 (s, 1H) .7.4-7.2 (m, 2H), 7.41 (d, 1H, J = 8.9 Hz) , 8.3 (m, 1H), 8.4 (m, 1H) Second Step: To a mixture of 3.8 g of an iron powder, 50 ml of acetic acid and 5 ml of water was added dropwise a solution of 3.8 g of 2-. { 2-Chloro-4-fluoro-5- [3-met-il-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -3-nitropi ridine in 5.0 ml acetic acid while maintaining the temperature of the reaction solution at 35 ° C or lower. After completion of the addition, the mixture was stirred for 2 hours, then, the reaction solution was filtered through Celite, and diluted with ethyl acetate. The mixture was neutralized with saturated aqueous sodium bicarbonate solution, the organic layer was washed with saturated saline solution, dried over anhydrous magnesium sulfate, and concentrated, then, the resulting residue was subjected to silica gel chromatography to obtain 3.4 g of 3-amino-2-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} pyridine. XH-NMR (CDC1./300 MHz) d (ppm): 3.53 (s, 3H), 4.00 (s, 2H), 6.34 (s, 1H), 6.82 (m, 1H), 6.99 (m, 1H), 7.29 (d, 1H, J = 6.7 Hz), 7.35 (d, 1H, J = 9.0 Hz), 7.47 (m, 1H) Step Three 0.76 ml of boron diethyl trifluoride etherate was added dropwise to a mixture of 3.4 g of 3-amino-2-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} pyridine, 3 ml of 1,2-dimethoxyethane and 1 ml of methylene chloride at -5 ° C, the mixture was stirred for 5 minutes, then 0.44 ml of t-butyl nitrite were added dropwise to the mixture, and the mixture was stirred for 30 minutes at the same temperature. The n-pentane was poured into the mixture, and 2.0 g of the precipitated crystals were collected by filtration. Subsequently, 200 mg of the crystals mentioned above were dissolved in 1 ml of acetic anhydride, and the mixture was stirred for 2 hours at 70 ° C. After removal of the solvent, the resulting residue was subjected to silica gel chromatography to obtain 89 mg of 3-acetoxy-2-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} pyridine. aH-NMR (CDC1./300 MHz) d (ppm): 2.43 (s, 3H), 3.55 (s, 3H), 6.35 (s, 1H), 7.05 (m, 1H), 7.21 (d, 1H, J = 6.9 Hz), 7.39 (d, 1H, J = 8.8 Hz), 7.47 (m, 1H), 7.97 (m, 1H) Step Four: A mixture of 100 mg of 3-acetoxy-2-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} pyridine, 15 mg of potassium carbonate and 1 ml of methanol was stirred for 3 hours at room temperature. The reaction solution was poured into ice water, then acetic acid was poured into it. The precipitated crystals were collected by filtration to obtain 65 mg of 2-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -3-hydroxypyridine Production Example 13: Production of compound 7-7 present Step One: 0.4 g of sodium hydride were added to a mixture of 1.59 g of 2-chloro-3-nitropyridine, 0.95 g of methyl glycolate and 10 ml of 1, 4-dioxane at 10 ° C. The mixture was stirred at room temperature for 2 hours, then, the reaction solution was poured into ice water, and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 1.5 g of 2- (methoxycarbonyl) methoxy-3-nitropyridine. Melting point: 61.5 ° C Step Two: A mixture of 0.3 g of 2- (methoxycarbonyl) methoxy-3-nitropyridine, 20 mg of platinum oxide and 1.4 ml of ethanol was stirred for 3 hours at room temperature under nitrogen atmosphere . The reaction system was purged with nitrogen, then, the reaction solution was filtered through Celite, and the filtrate was concentrated. The residue was subjected to silica gel column chromatography to obtain 0.22 g of 3-amino-2- (methoxycarbonyl) methoxypyridine. aH-NMR (CDC1./250 MHz) d (ppm): 3.77 (s, 3H), 3.85 (bs, 2H), 4.95 (s, 2H), 6.75 (dd, 1H, J = 7.5, 5.0 Hz), 6.91 (dd, 1H, J = 7.5, 1.6 Hz), 7.50 (dd, 1H, J = 5.0, 1.6 Hz) Step Three: 1.6 g of boron diethyl trifluoride etherate were added dropwise to a mixture of 1.0 g of 3-amino-2- (methoxycarbonyl) methoxypyridine, 3 ml of 1,2-dimethoxyethane and 1 ml of dichloromethane at -10 ° C. The mixture was stirred for 10 minutes at the same temperature, then a solution of 0.68 g of t-butyl nitrite in 1 ml of 1,2-dimethoxyethane at -5 ° C or more was added dropwise to the reaction solution. low. The mixture was stirred for 30 minutes at the same temperature, then n-pentane was poured into the mixture. The lower layer of the two separated layers was dissolved in 5 ml of acetic anhydride, and the mixture was stirred for 1 hour at 80 ° C. The solvent was distilled off, then the resulting residue was subjected to silica gel chromatography to obtain 0.45 g of 3-acetoxy-2- (methoxycarbonyl) methoxypyridine. ^ -NMR (CDCl3 / 250 MHz) d (ppm): 2.33 (s, 3H), 3.75 (s, 3H), 4.92 (s, 2H), 6.93 (dd, 1H, J = 7.7, 5.0 Hz), 7.38 (dd, 1H, J = 7.7, 1.6 Hz), 7.97 (dd, 1H, J = 5.01, 1.6 Hz) The follow-on was prepared in a similar manner. 3-Acetoxy-2- (methoxycarbonyl) methylthiopyridine aH-NMR (CDCl 3 / 25O MHz) d (ppm): 2.36 (s, 3 H), 3.74 (s, 3 H), 4.00 (s, 2 H), 7.07 (dd, 1 H) , J = 8.0, 4.7 Hz), 7.37 (dd, 1H, J = 8.0, 1.5 Hz), 8.29 (dd, 1H, J = 4.7, 1.5 Hz) Step Four: A mixture of 0.1 g of 3-acetoxy-2- (methoxycarbonyl) methoxypyridine, 31 mg of potassium carbonate and 1 ml of methanol was stirred for 3 hours at room temperature. The reaction solution was poured into water, and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 73 mg of 3-hydroxy-2- (methoxycarbonyl) methoxypyridine. H-NMR (CDC1./250 MHz) d (ppm): 3.78 (s, 3H), 4.98 (s, 2H), 6.84 (dd, 1H, J = 7.7, 5.0 Hz), 7.17 (dd, 1H, J = 7.7, 1.3 Hz), 7.63 (dd, lH, J = 5.0, 1.3 Hz) The follow-up was prepared in a similar manner. 3-hydroxy-2- (methoxycarbonyl) methylthiopyridine 1H-NMR (CDC1./250 MHz) d (ppm): 3.74 (s, 3H), 3.92 (s, 2H), 7.02 (dd, 1H, J = 8.1, 4.6 Hz), 7.13 (d, 1H, J = 8.1 Hz), 8.06 (d, 1H, J = 4.6, Hz) The following is prepared in a similar manner. 3-hydroxy-2- (ethoxycarbonyl) methylthiopyridine.
Step Five: To a mixture of 0.29 g of 3-hydroxy-2- (methoxycarbonyl) methoxypyridine, 0.23 gd 2, 5-difluoro-4- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1, 2,3,6-tetrahydropyrimidin-1-yl] nitrobenzene and 3.2 ml of N, N-dimethylformamide were added 0.11 g of potassium carbonate, and the mixture was stirred for 2 hours at 70 ° C. 0.12 g of 2,5-difluoro-4- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] nitrobenzene and 0.05 g of potassium carbonate they were added further, and the mixture was stirred for 1 hour at 70 ° C. The solution was cooled to room temperature, poured into ice water, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.39 g of 3-. { 4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] -2-nitrophenoxy} -2- (methoxycarbonyl) methoxypyridine [compound 9-45 present]. XH-NMR (CDC1./250 MHz) d (ppm): 3.51 (q, 3H, J = 1. 1 Hz), 3.68 (s, 3H), 4.86 (d, 1H), 4.98 (d, 1H), 6.29 (s, 1H), 6.99 (dd, 1H, J = 7.8, 4.9 Hz), 7.11 (d, 1H, J = 6. 0 Hz), 7.51 (dd, 1H, J = 7.8, 1.6 Hz), 7.87 (d, 1H, J = 8.6 Hz), 7.99 (dd, 1H, J = 4.9, 1.6 Hz) The follow-up was prepared in a similar manner. 3-. { 4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] -2-nitrophenoxy} -2- (methoxycarbonyl) methylthiopyridine aH-NMR (CDCl3 / 300 MHz) d (ppm): 3.54 (s, 3H), 3.73 (s, 3H), 4.01 (s, 2H), 6.33 (s, 1H), 7.0 -7.1 (m, 2H), 7.18 (dd, 1H, J = 7.8, 1.3 Hz), 7.92 (d, 1H, J = 8.5 Hz), 8.28 (dd, 1H, J = 4.4, 1.3 Hz) The following is prepared in a similar way. 3-. { 4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] -2-nitrophenoxy} -2- (Ethoxycarbonyl) methylthiopyridine Step Six: To a mixture of 0.3 g of an iron powder, 3 ml of acetic acid and 0.3 ml of water was added dropwise a solution of 0.30 g of 3-. { 4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] -2-nitrophenoxy} -2- (methoxycarbonyl) methoxypyridine [compound 9-45 present] in 2 ml of acetic acid while maintaining the temperature of the reaction solution at 35 ° C or lower. After completion of the addition, the mixture was stirred for 2 hours, then, the reaction solution was filtered through Celite, and diluted with ethyl acetate. The mixture was neutralized with saturated aqueous sodium bicarbonate solution, the organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated, then, the resulting residue was subjected to silica gel column chromatography. to obtain 0.24 g of 3-. { 2-amino-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (methoxycarbonyl) methoxypyridine. aH-NMR (CDCl3 / 250 MHz) d (ppm): 3.52 (s, 3H), 3.74 (s, 3H), 4.29 (s, 2H), 5.00 (s, 2H), 6.30 (s, 1H), 6.61 (d, 1H, J = 11.3 Hz), 6.76 (d, 1H, J = 6.8 Hz), 6.86 (dd, 1H, J = 7.8, 5.0 Hz), 7.22 (dd, 1H, J = 7.8, 1.1 Hz) , 7.82 (dd, 1H, J = 5.0, 1.1 Hz) The follow-up was prepared in a similar manner. 3-. { 2-amino-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} 2- (methoxycarbonyl) methylthiopyridine XH-NMR (CDCl3 / 250 MHz) d (ppm): 3.53 (s, 3H), 3.75 (s, 3H), 4.02 (s, 2H), 4.18 (bs, 2H), 6.32 (s, 1H), 6.66 (d, 1H, J = 10.7 Hz), 6.82 (d, 1H, J = 6.7 Hz), 6.95 (dd, 1H, J = 8.4, 4.9 Hz), 7.03 (dd, 1H, J = 8.4, 1.4 Hz), 8.14 (dd, 1H, J = 4.9, 1.4 Hz) Step Seven: 88 mg of isoamyl nitrite were added dropwise to a mixture of 0.24 g of 3-. { 2-amino-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (methoxycarbonyl) methoxypyridine, 99 mg copper chloride (II), 0.20 g of copper (II) chloride and 2.5 ml of acetonitrile at room temperature, and the mixture was stirred for 1 hour. This reaction solution was poured into 2% hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.21 g of 3-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (methoxycarbonyl) methoxypyridine [compound 7-7 present]. Melting point: 52.2 ° C XH-NMR (CDCl3 / 300 MHz) d (ppm): 3.50 (q, 3H, J = 1.0 Hz), 3.70 (s, 3H), 4.90 (d, 1H, J = 15.8 Hz ), 4.97 (d, 1H, J = 15.8 Hz), 6.29 (s, 1H), 6.9-7.0 (m, 2H), 7.32 (dd, 1H, J = 7.7, 1.9 Hz), 7.37 (d, 1H, J = 8.7 Hz), 7.92 (dd, 1H, J = 4.9, 1.9 Hz) The follow-on was prepared in a similar manner. 3-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3, β-tetrahydropyrimidin-1-yl] phenoxy} -2- (methoxycarbonyl) methylthiopyridine [compound 7-27 present] XH-NMR (CDCl3 / 300 MHz) d (ppm): 3.54 (s, 3H), 3.75 (s, 3H), 4.01 (s, 2H), 6.33 (s, 1H), 6.9-7.0 (m, 3H), 7.42 (d, 1H, J = 9.0 Hz), 8.20 (dd, 1H, J = 4.1, 2.2 Hz) The following is prepared in a similar manner. 3-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (ethoxycarbonyl) methylthiopyridine [compound present 7-28] Production Example 14 Production of compound 4-85 present Step One: 68 mg of sodium hydride were added to a mixture of 0. 4 g of 5-benzyloxy-4-chloro-2-methylpyrimidine, 0.17 g of methyl glycolate and 3.4 m of tetrahydrofuran at 0 ° C. The mixture was stirred at room temperature for 1 hour, then, the reaction solution was stirred for 30 minutes at 90 ° C. 18 mg of methyl glycolate was added thereto, and the mixture was stirred for 30 minutes at 90 ° C. The reaction solution was cooled to room temperature, then, it was poured into ice water, and extracted with ethyl acetate. The organic layer was washed with dilute hydrochloric acid and saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.21 g of 5-benzyloxy-4- (methoxycarbonyl) methoxy-2-methylpyrimidine. -.- I-NMR (CDC1./300 MHz) d (ppm): 2.49 (s, 3H), 3.78 (s, 3H), 5.01 (s, 2H), 5.17 (s, 2H), 7.2-7.5 ( m, 5H), 7.99 (s, 1H) Step Two: A mixture of 0.21 g of 5-benzyloxy-4 - (meth oxycarbonyl) met oxy-2-met ilpyrimidine, 16 mg of palladium / 10% carbon and 1.5 ml of ethyl acetate was stirred for 3 hours at room temperature under nitrogen atmosphere. The reaction system was purged with nitrogen, then, the reaction solution was filtered through Celite, and the filtrate was concentrated to obtain 0.15 g of 5-hydr oxy-4 - (me t-oxycarboni 1) me t-oxy-2 -methylpyrimidine. XH-NMR (CDC1./300 MHz) d (ppm): 2.51 (s, 3 H), 3.81 (s, 3 H), 5.00 (s, 2 H), 8.10 (s, 1 H) Step Three: To a mixture of 0.15 g of 5-hydroxy-4- (me t-oxycarbonyl) me t-oxy-2-met ilpyr imidine, 0.16 g of 2,5-difluoro-4- [3-methyl-2,6-dioxo- 4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] nitrobenzene and 2 ml of N-dimethyl formamide were added with 74 mg of potassium carbonate, and the mixture was stirred for 1 hour at room temperature. 70 ° C. The reaction solution was cooled to room temperature, then, poured into ice water, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.20 g of 5-. { 4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] -2-nitrophenoxy} -4 - (methoxycarbonyl) methoxy-2-methylpyrimidine. Melting point: 149.5 ° C Fourth Step A mixture of 0.19 g of 5-. { 4-f luoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tet, rahydropyrimidin-1-yl] -2-nitrophenoxy} - 4 - (methoxycarbonyl) methoxy-2-met ilpyrimidine, 5 mg of platinum oxide, 2 ml of ethanol and 2 ml of ethyl acetate were stirred for 1.5 hours at room temperature under nitrogen atmosphere. The reaction system was purged with nitrogen, then, the reaction solution was filtered through Celite, and the filtrate was concentrated to obtain 0.17 g of 5 -. { 2-amino-4-fluoro-5- [3-methyl-2,6-di-oxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -4- (methoxycarbonyl) me toxy-2-methylpyrimidine. XH-NMR (CDC1./300 MHz) d (ppm): 2.55 (s, 3 H), 3.51 (s, 3 H), 3.75 (s, 3 H), 4.9-5.1 (m, 2 H), 6.30 (s, 1 H) ), 6.67 (d, 1H, J = 6.3 Hz), 6.83 (bs, 1H), 7.15 (d, 1H, J 11.0 Hz 7.42 (bs, 1H), 8.18 (s, 1H) Fifth Step 60 mg of isoamyl nitrite were added dropwise to a mixture of 0.17 g of 5-. { 2-amino-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,6,6-tetrahydropyrimidin-1-yl] phenoxy} -4- (methoxycarbonyl) methoxy-2-met ilpyr imidine, 67 mg of copper (I) chloride, 137 mg of copper (II) chloride and 2 ml of acetonitrile at room temperature, and the mixture was stirred for 1 hour . This reaction solution was poured into 2% hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 20 mg of 5-. { 2-Chloro-4-fluoro-5- [3-methyl-1-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -4- (methoxycarbonyl) methoxy-2-met i lpyrimidine [compound 4-85 present]. 1 H-NMR (CDCl 3/300 MHz) d (ppm): 2.57 (s, 3H), 3.51 (q, 3H, J = 1.1 Hz), 3.71 (s, 3H), 4. 90 (d, 1H, J = 15.7 Hz), 5.00 (d, '1 H, J = 15.7 Hz), 6.29 (s, 1H), 6.89 (d, 1H, J = 6.4 Hz), 7. 37 (d, 1H, J = 9.0 Hz), 8.26 (s, 1H) Production Example 15 Production of compound 4-76 present First step: Sodium hydride was added to a mixture of 5-benzyl-1-oxy-4-chloro-2-methyl-1-pyrimidine, methyl lactate and tetrahydrofuran at 0 ° C. The mixture was stirred at room temperature for 1 hour, then, it was stirred at 90 ° C for 30 minutes. The reaction solution was cooled to room temperature and poured into ice water, and extracted with ethyl acetate. The organic layer was washed with dilute hydrochloric acid and saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 5-benzyloxy-4-. { 1- (methoxycarbonyl) ethoxy} -2-methylpyrimidine.
Step Two A mixture of 5-benz 1 oxy-4 -. { 1- (methoxycarbonyl) ethoxy} -2-methylpyrimidine, palladium / 10% carbon and ethyl acetate was stirred for 3 hours at room temperature under nitrogen atmosphere. The reaction system was purged with nitrogen, then, the reaction solution was filtered through Celite, and the filtrate was concentrated to obtain 5-hydroxy-4-. { 1- (methoxycarbonyl) ethoxy} -2-methylpyrimidine.
Step Three: To a mixture of 5-hydroxy-4 -. { 1- (methoxycarbonyl) ethoxy} -2-methylpyrimidine, 2,5-difluoro-4- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] nor trobenzene and N, N-dimyl-1-formamide was added potassium carbonate, and the mixture was stirred for 1 hour at 70 ° C. The reaction solution was cooled to room temperature, then, poured into ice water, and extracted with ethyl acetate. The organic layer was washed with saturated saline solution, dried over sodium sulfate, and dried. of anhydrous magnesium, and concentrated. The residue was subjected to silica gel column chromatography to obtain 5-. { 4-fluoro-5 .- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] -2-nitrophenoxy} -4-. { 1- (methoxycarbonyl) ethoxy} -2-methylpyrimidine.
Step Four: A mixture of 5-. { 4-Fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] -2-nitrophenoxy} -4-. { 1 - (methoxycarbonyl 1) ethoxy} -2-methylpyrimidine, platinum oxide, ethanol and ethyl acetate was stirred for 1.5 hours at room temperature under nitrogen atmosphere. The reaction system was purged with nitrogen, then, the reaction solution was filtered through Celite, and the filtrate was concentrated to obtain 5-. { 2-amino-4-fluoro-5- [3-met-il-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -4- . { 1- (methoxycarbonyl) ethoxy} -2-methylpyrimidine.
Step Five: Isoamyl nitrite was added dropwise to a mixture of 5 -. { 2-amino-4-f 1 -ooro-5 - [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -4- . { 1 - (methoxy carbonyl) ethoxy} -2-methylpyrimidine, copper (I) chloride, copper (II) chloride and acetonitrile at room temperature, and the mixture was stirred for 1 hour. This reaction solution was poured into 2% hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 5-. { 2-Chloro-4-fluoro-5- [3-methyl-1-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -4-. { 1- (methoxycarbonyl) eto ^ i} -2-methylpyrimidine [compound 4-76 present].
Production Example 16 Production of compound 7-2 present Step One: 0.8 g of sodium hydride were added to a mixture of 3.17 g of 2-chloro-3-nitr opi idine, 2.19 g of methyl lactate and 20 ml of 1,4-dioxane at 10 ° C. The mixture was stirred at room temperature for 1.5 hours, then, poured into ice water, and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 3.3 g of 2-. { 1- (methoxycarbonyl) ethoxy} -3-nitropyridine. XH-NMR (CDCl3 / 300 MHz) d (ppm): 1.70 (d, 3H, J = 7.0 Hz), 3.74 (s, 3H), 5.4'6 (q, 1H, J = 7.0 Hz), 7.07 (dd) , 1H, J = 7.8, 5.0 Hz), 8.2-8.4 (m, 2H) Second Step: A mixture of 1.7 g of 2-. { 1- (methoxycarbonyl) ethoxy} - 3 - Nitric oxide, 102 mg of platinum oxide and 7.5 ml of ethanol was stirred for 3.5 hours at room temperature under nitrogen atmosphere. The reaction system was purged with nitrogen, then, the reaction solution was filtered through Celite, and the filtrate was concentrated. The residue was subjected to silica gel column chromatography to obtain 1.16 g of 3-amino-2 -. { 1- (methoxycarbonyl) ethoxy} pyridine. 1 H-NMR (CDCl 3/300 MHz) d (ppm): 1.63 (d, 3 H, J = 6.8 Hz), 3.74 (s, 3 H), 3.84 (bs, 2 H), 5.38 (d, 1 H, J = 6.8 Hz ), 6.72 (dd, 1H, J = 7.7, 5.0 Hz), 6.90 (dd, 1H, J = 7.7, 1.4 Hz), 7.48 (dd, 1H, J = 5.0, 1.4 Hz) Step Three 1. 5 ml of boron diethyl trifluoride etherate were added dropwise to a mixture of 1.1 g of 3-amino-2 -. { 1 - (me t oxycarboni 1) ethoxy} pi ridine, 3 ml of 1,2-dimethoxyethane and 1 ml of dichloromethane at -10 ° C.
After mixing for 10 minutes at the same temperature, a solution of 0.80 ml of t-butyl nitrite in 1 ml of 1,2-dimethoxyethane was added dropwise to the reaction solution at -5 ° C or less . After mixing for 30 minutes at the same temperature, n-pentane was poured into the mixture. The lower layer of two separate layers was dissolved in 5 ml of acetic anhydride, and the mixture was stirred for 1 hour at 70 ° C. The solvent was distilled off, then the resulting residue was subjected to silica gel chromatography to obtain 0.34 g of 3-acetoxy-2-. { 1- (methoxycarbonyl) ethoxy} pyridine. XH-NMR (CDC1./300 MHz) d (ppm): 1.60 (d, 1H, J = 7.0 Hz), 2.33 (s, 3H), 3.73 (s, 3H), 5.34 (q, 1H, J = 7.0 Hz), 6.91 (dd, 1H, J = 7.6, 5.0 Hz), 7.36 (dd, 1H, J = 7.6, 1.5 Hz), 7.97 (dd, 1H, J = 5.0, 1.5 Hz) Fourth Step A mixture of 0.34 g of 3 -acet oxy-2 -. { 1 - (methoxycarbonyl 1) ethoxy} pi Ridin, 0.11 g of potassium carbonate and 2 ml of methanol was stirred for 1 hour at room temperature. The reaction solution was poured into water, and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 190 mg of 3-hydroxy-2-. { 1- (methoxycarbonyl) ethoxy Jpyridine. XH-NMR (CDCl3 / 300 MHz) d (ppm): 1.64 (d, 1H, J = 7.0 Hz), 3.75 (s, 3H), 5.45 (q, 1H, J = 7.0 Hz), 6.0-6.2 (bs) , 1H), 6.83 (dd, 1H, J = 7.7, 5.0 Hz), 7.15 (dd, 1H, J = 7.7, 1.5 Hz), 7.63 (dd, 1H, J = 5.0, 1.5 Hz) Step Five: To a mixture of 0.18 g of 3-hydroxy-2-. { 1 - (methoxycarbonyl) ethoxy} pyridine, 0.19 g of 2,5-di-fluoro-4- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] nitrobenzene and 2.0 ml of, N-dimet ilformamide was added 91 mg of potassium carbonate, and the mixture was stirred for 3 hours at 70 ° C. The reaction solution was cooled to room temperature, then, poured into ice water, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.21 g of _ 3-. { 4-Fluoro-5- [3-met il-2, 6-dioxo-4 - (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] -2-nitrophenoxy} -2-. { 1- (methoxycarbonyl) ethoxy} pi ridine [compound 9-42 present] (as a mixture of two isomers, diastereomers). 1 H-NMR (CDCl 3/300 MHz) d (ppm): 1.45 (d, 3/2 H, J = 7.1 Hz), 1.46 (d, 3/2 H, J = 7.1 Hz), 3.49 (s, 3/2 H) , 3.51 (s, 3 / 2H), 3.66 (s, 3H), 5.29 (q, 1 / 2H, J = 7.1 Hz), 5.31 (q, 1 / 2H, J = 7.1 Hz), 6.28 (s, 1 / 2H), 6.30 (s, 1 / 2H), 6.9-7.0 (m, 1H), 7.10 (d, 1 / 2H, J = 6.1 Hz), 7.17 (d, 1 / 2H, J = 6.1 Hz), 7.4-7.6 (m, 1H), 7.8-7.9 (m, 1H), 7.9-8.0 (m, 1H).
Sixth Step: A solution of 3- was added dropwise to a mixture of 0.21 g of an iron powder, 3 ml of acetic acid and 0.3 ml of water. { 4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] -2-nitrophenoxy} -2-. { 1- (methoxycarbonyl) ethoxy} pyridine [compound 9-42 present] in 2 ml of acetic acid while maintaining the temperature of the reaction solution at 35 ° C or lower. After the completion of the. addition, the mixture was stirred for 1 hour, then, the reaction solution was filtered through Celite, and diluted with ethyl acetate. The mixture was neutralized with saturated aqueous sodium bicarbonate solution, the organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated, then, the resulting residue was subjected to silica gel chromatography to obtain 0.16 g of 3-. { 2-amino-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2-. { 1- (methoxycarbonyl) e t o'xi} pyridine (as a mixture of two isomeric teresomers). 1 H-NMR (CDCl 3/300 MHz) d (ppm): 1.61 (d, 3 H, J = 7.1 Hz), 3.52 (s, 3 H), 3.72 (s, 3 H), 4.28 (bs, 2 H), 5.40 (q , 1 / 2H, J = 7.1 Hz), 5.41 (q, 1 / 2H, J = 7.1 Hz), 6.30 (s, 1H), 6.62 (d, 1H, J = 10.9 Hz), 6.7-6.8 (m, 1H), 6.8-6.9 (m, 1H), 7.2-7.3 (m, 1H), 7.7-7.9 (m, 1H) Seventh Step 18 mg of isoamyl nitrite was added dropwise to a mixture of 0.16 g of 3-. { 2-amino-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydro-rimidin-1-yl] phenoxy} -2-. { 1- (methoxycarbonyl) ethoxy} pyridine, 63 mg of copper (I) chloride, 129 mg of copper (II) chloride and 1.5 ml of acetonitrile at 0 ° C, and the mixture was stirred for 10 minutes, then at room temperature for 1 hour. This reaction solution was poured into a mixture of IN hydrochloric acid and ice, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.12 g of 3-. { 2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2, "3,6-tetrahydropyrimidin-1-yl] phenoxy] -2-. (1) (me toxi ca rboni 1) e toxi.. Pi ri dina (as a mixture of two isomers di ast e er me ri co) [compound 7-2 present]. 1 H-NMR (CDC1./300 MHz) d (ppm): 1.51 (d, 3 / 2H, J = 7.0 Hz), 1.52 (d, 3 / 2H, J = 7.0 Hz), 3.50 (s, 3H), 3.67 (s, 3H), 5.29 (q, 1 / 2H, J = 7.0 Hz), 5.30 (q, 1 / 2H, J = 7.0 Hz), 6.28 (s, 1 / 2H), 6.29 (s, 1 / 2H), 6.8-7.0 (m , 2H), 7.3-7.4 (m, 2H), 7.8-7.9 (m, 1H) Production Example 17 Production of compound 4-7 present First step To a mixture of 0.297 g of sodium hydride and N, N-dimethyl t-formamide, 0.668 g of methyl glycolate was added and stirred at room temperature for 1 hour. The mixture was then added to the mixture 5-bis i 1 oxy-4-chlor opidimidine (produced as follows: mixture A of 1.5 g of 5-benzyl-1-oxy-4-pyrimidone and 30 ml of chloride of phosphoryl was stirred for 30 minutes at reflux temperature, then the mixture was cooled to room temperature and concentrated, ice water was added to the residue, extracted with ether and concentrated.), and stirred for 3 hours at room temperature. room temperature. The mixture was poured into saturated ammonium chloride solution, and extracted with ethyl acetate. The organic layer was washed with saturated ammonium chloride solution and saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.934 g of 5-benzyloxy-4 (methoxycarbonyl) methoxypyrimidine. Melting point: 78.7 ° C Second Step: A mixture of 0.9 g of 5-benzyloxy-4- (methoxycarbonyl) methoxypyrimidine, 10% palladium / carbon and ethyl acetate was stirred for 3 hours at room temperature under nitrogen atmosphere. The reaction system was purged with nitrogen, then, the reaction solution was filtered through Celite, and the filtrate was concentrated to obtain 0.574 g of 5-hydroxy-4- (methoxycarbonyl) methoxypyrimidine. Melting point: 105.0 ° C Step Three: To a mixture of 42 mg of sodium hydride and N, N-dimethyl-1-formamide, 0.184 g of 5-hydroxy-4- (methoxycarbonyl) methyloxypropionate was added and stirred at room temperature. 1 hour. Then 0.35 of 2,5-difluoro-4- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] nitrobenzene was added to the mixture, and it was stirred for 2 hours at room temperature, then for 1 hour at 50 ° C. The mixture was poured into saturated ammonium chloride solution, and extracted with acetate. 'of ethyl. The organic layer was washed with saturated ammonium chloride solution and saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.448 g of 5-. { 4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] -2-nitrophenoxy} -4 - (methoxycarbonyl) methoxypyrimidine. Melting point: 55.7 ° C Step Four To a mixture of 0.4 g of an iron powder, 2 ml of acetic acid and 0.2 ml of water was added dropwise a solution of 0.393 g of 5-. { 4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] -2-ni t-rofenoxi} -4 - (methoxycarbonyl) methoxypyrimidine in 1 ml of acetic acid and 2 ml of ethyl acetate. After the completion of the addition, the mixture was stirred for 1 hour at room temperature, for 2 hours at 30-40 ° C. Water was added to the mixture, then, the mixture was filtered through Celite, and extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium bicarbonate solution, and saturated saline, dried over anhydrous magnesium sulfate, and concentrated. Then, the resulting residue was subjected to silica gel chromatography to obtain 0.315 g of 5-. { 2-amino-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -4- (methoxycarbonyl) methoxypyrimidine. Melting point: 71.2 ° C Step Five: A solution of 0.228 g of isoamyl nitrite in acetonitrile was added dropwise to a mixture of 0.315 g of 5 -. { 2-amino-4-fluoro-5 - [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -4- (methoxycarbonyl) methoxypyrimidine, 0.129 g of copper (I) chloride, 0.262 g of copper (II) chloride and acetonitrile a. room temperature, and the mixture was stirred for 3 hours. The mixture was concentrated, diluted with ethyl acetate, filtered, through Celite. To the filtrate, water was added, then extracted with ethyl acetate. The organic layer was washed with 1% hydrochloric acid, and saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 5-. { 2-chloro-4-f luoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -4 - (I t oxi carboni 1) me t oxipi r imi di na [compound 4-7 present]. Melting point: 52.5 ° C Production Example 1 Produces ion of compound 4-2 present First step: Sodium hydride was added to a mixture of 5-benzyl-1-oxy-4-chloropyridine, methylcartate and tetrahydrofuran at 0 ° C. The mixture was stirred at room temperature for 1 hour, then stirred for 30 minutes at 90 ° C. The reaction solution was cooled to room temperature, then, poured into ice water, and extracted with ethyl acetate. The organic layer was washed with dilute hydrochloric acid and saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 5-benzyloxy- 4 -. { 1- (methoxycarbonyl) ethoxy} pyrimidine.
Step Two A mixture of 5-benz 1 ox i - 4 -. { 1- (methoxycarbonyl) ethoxy} pyrimidine, palladium / 10% carbon and ethyl acetate was stirred for 3 hours at room temperature under a hydrogen atmosphere. The reaction system was purged with nitrogen, then, the reaction solution was filtered through Celite, and the filtrate was concentrated to obtain 5-hydroxy-4-. { 1- (methoxycarbonyl) ethoxy} pyrimidine.
Step Three: To a mixture of 5-hydroxy-4-. { 1- (methoxycarbonyl 1) ethoxy} pyrimidine, 2,5-difluoro-4- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] nor trobenzene and N, N-dimethylformamide potassium carbonate was added, and the mixture was stirred for 1 hour at 70 ° C. The reaction solution was cooled to room temperature, then, poured into ice water, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 5-. { 4-Fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] -2-n-t-rofenoxi} -4- . { 1- (methoxycarbonyl) ethoxy Jpyrimidine.
Step Four A mixture of 5-. { 4-f luoro-5- [3-met il-2, 6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] -2-nitrophenoxy} -4-. { 1 - (methoxycarbonyl) ethoxy} pyrimidine, platinum oxide, ethanol and ethyl acetate was stirred for 1.5 hours at room temperature under a hydrogen atmosphere. The reaction system was purged with nitrogen, then, the reaction solution was filtered through Celite, and the filtrate was concentrated to obtain 5 -. { 2-amino-4-f luor o- 5 - [3-methyl-2,6-dioxo-4-. { 1- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} - 4 - (methoxy carbonyl) ethoxy} pyrimidine.
Fifth Step Isoamyl nitrite was added dropwise to a mixture of 5 -. { 2-amino-4-f luoro-5 - [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -4-. { 1- (methoxycarbonyl) ethoxy} pyrimidine, copper (I) chloride, copper (II) chloride and acetonitrile at room temperature, and the mixture was stirred for 1 hour. This reaction solution was poured into 2% hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 5 -. { 2-chloro-4-f luoro-5 - [3-methyl-2,6-dioxo-4- (tr'-trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -4-. { 1 - (me t oxycarboni 1) et oxy} pi r imidine [compound 4-2 present] Production Example 19: Production of compound 7-42 present First step: To a mixture of 0.385 g of sodium hydride and dimethyl sulfoxide, a solution of 1.04 g of benzyl alcohol in dimethyl sulfoxide was added at room temperature. Then the mixture was stirred for 30 minutes at 50 ° C, and cooled to room temperature. A solution of 1.7 g of 4-bromo-3-me t oxime t oxypyridine (produced by the method described in Tetrahedron, 12745-12774, (1998)) in dimethyl sulfoxide was added to the mixture, and the mixture was added to the mixture. stirred for 2 hours at 50-60 ° C. The mixture was poured into water, and extracted with ethyl acetate. The organic layer was washed with water, then saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to UTOna colony chromatography on silica gel to obtain 4-benzyloxy-3-methoxymethoxypyridine. Melting point: 71.2 ° C Step Two A mixture of 0.7 g of 4-benzylloxy-3-methoxymethoxypyridine and IN hydrochloric acid was stirred for 2 hours at 60 ° C. The mixture was poured into saturated aqueous sodium bicarbonate solution, extracted with ethyl acetate. The organic layer was washed with saturated saline solution, dried over anhydrous magnesium sulfate, concentrated to obtain 0.547 g of 4-benzyloxy-3-hydroxypyridine. Melting point: 173.0 ° C Step Three To a mixture of 57 mg of sodium hydride and N, N-dimethyl-1-ormamide, 0.286 g of 4-benzyloxy-3-hydroxypiine was added and stirred at room temperature for 30 minutes. Then 0.5 g of 2, 5 -di f luor or- 4 - [3-methyl-2, 6-dioxo-4- (trifl uorome t il) -1,2, 3,6-tetrahydropyrimidine- were added. 1 -yl] or trobenzene to the mixture, and stirred for 1 hour at room temperature, then, for 1 hour at 50-60 ° C. The mixture was poured into saturated ammonium chloride solution, and extracted with ethyl acetate. The organic layer was washed with saturated ammonium chloride solution and saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.548 g of 4-benzyloxy-3-. { 4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,6,6-tetrahydropyrimidin-1-yl] -2-nitrophenoxy} pyridine. 23. 7 nD 1.5497 Step Cua rto: A solution of 0.548 g of 4-benzyloxy-3- [4-fluoro-5- [3-methyl] was added dropwise to a mixture of 0.55 g of an iron powder, 3 ml of acetic acid and 0.3 ml of water. -2,6-dioxo-4- (trifluoromethyl) -1,2,6,6-tetrahydropyrimidin-1-yl] -2-nitro-enoxi} pyr'dine in 0.5 - ml of acetic acid and 3 ml of ethyl acetate. After the completion of the addition, the mixture was stirred for 3 hours at 40-50 ° C. The mixture was poured into water, then, the mixture was filtered through Celite, and extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium bicarbonate solution, and saturated saline, dried over anhydrous magnesium sulfate, and concentrated, to obtain 0.438 g of 3 -. { 2-ami no-4-f 1 uo ro- 5 - [3 -me t i 1 -2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -4-benzyloxypyridine. Melting point: 69.3 ° C Fifth Step A solution of 0.307 g of isoamyl nitrite in acetonitrile was added dropwise to a mixture of 0.438 g of 3 -. { 2-amino-4-f luoro-5 - [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} 4-benzyloxypyridine, 0.173 g of copper (I) chloride, 0.352 g of copper (II) chloride and acetonitrile at room temperature, and the mixture was stirred for 1 hour. On the next day, the mixture was concentrated, diluted with water and ethyl acetate, filtered through Celite. The filtrate was extracted with ethyl acetate. The organic layer was washed with 1% hydrochloric acid, and saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.362 g of 4-benzyloxy-3- (2-chloro-4-f luoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) ) - 1, 2, 3, 6-tetrahydropyrimidin-1-yl] phenoxy, pyridine, melting point: 55.0 ° C Sixth Step A mixture of 0.356 g of 4 -benz i 1 ox i - 3 -. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} pyridine, palladium / 10% carbon and ethyl acetate was stirred for 8 hours at room temperature under a hydrogen atmosphere. The reaction system was purged with nitrogen, then, the reaction solution was filtered through. Celite, and the filtrate was concentrated to obtain 0.32 g of 3-. { 2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} - 4-Hydroxypyridine. Melting point: 196.1 ° C Sép t imo step To a mixture of 30 mg of sodium hydride and N, N-dimethyl t-formamide, 0.31 g of 3 - was added. { 2-Chloro-4-f-1 -or- 5 - [3 -me t i 1 -2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} 4-hydroxypyridine and stirred at room temperature for 1 hour. Then, 0.114 g of methyl bromoacetate was added to the mixture, and it was stirred for 8 hours at room temperature. The mixture was poured into saturated ammonium chloride solution, and extracted with ethyl acetate. The organic layer was washed with saturated ammonium chloride solution and saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 27 mg of 3-. { '2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -4 - (methoxycarbonyl) met oxypyridine [compound 7-42 present]. 1 H-NMR (CDCl 3/250 MHz) d (ppm): 3.51 (q, 3 H, J = 1.2 Hz), 3.74 (s, 3 H), 4.71 (s, 2 H), 6.29 (s, 1 H), 6.7-6.8 (m, 2H), 7.37 (d, 1H, J = 8.8 Hz), 8.35 (d, 1H, J = 5.5 Hz), 8.37 (s, 1H) Production Example 20 Production of compound 2-45 present First step: 2. 0 g of sodium hydride were added to a mixture of 9.65 g of 2,6-di-chloro-3-n-tropiridine, 4.95 g of methyl glycolate and 100 ml of tetrahydrofuran at 0 ° C. The mixture was stirred at 0 ° C for 4 hours. The reaction solution was poured into ice water, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 10.86 g of 6-chloro-2- (methoxy carboni 1) methoxy-3-nitropyridine. XH-NMR (CDCl3 / 300 MHz) d (ppm): 3.80 (s, 3H), 5.09 (s, 2H), 7.11 (d, 1H, J = 8.4 Hz), 8.34 (d, 1H, J = 8.4 Hz ), Step Two A mixture of 1.0 g of 6-chloro-2- (methoxycarboni 1) met oxy-3-nitropyridine, 1.37 g of 2-chloro-4-fluoro-5- [3-methyl-2,6- dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenol, 0.67 g of potassium carbonate and 5 ml of N, -dime ti 1 fo rmamide was stirred for 1 hour at room temperature , then at 50 ° C for 30 minutes. The resulting residue was added to ice water, extracted with ethyl acetate, and the organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 2.25 g of 6-. { 2-cl or o- 4-f luoro-5 - [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (methoxycarbonyl) methoxy-3-nitropyridine. 1 H-NMR (CDCl 3 '/ 250 MHz) d (ppm): 3.56 (s, 3H), 3.64 (s, 3H), 4.81 (s, 2H), 6.36 (s, 1H), 6. 75 (d, 1H, J = 8.6 Hz), 7.14 (d, 1H, J = 6.6 Hz), 7.41 (d, 1H, J = 8.9 Hz), 8.52 (d, 1H, J = 8.6 Hz), Step Three A mixture of 2.25 g of 6-. { 2-c 1 or r o- 4 -fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (met oxycarbon 1) methoxy-3-nitropyridine, 0.3 g palladium / 10% carbon and 40 ml ethyl acetate was stirred for 3 hours at room temperature under a hydrogen atmosphere. The reaction system was purged with nitrogen, then, the reaction solution was filtered through Celite, and the filtrate was concentrated. The residue was subjected to silica gel column chromatography to obtain 1.38 g of 3-ami no-6 -. { 2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (methoxycarbonyl) methoxypyridine. X H-NMR (CDCl 3/250 MHz) d (ppm): 3.54 (s, 3 H), 3.6-3.7 (b, 2 H), 3.67 (s, 3 H), 4.76 (s, 2 H), 6.33 (s, 1 H) ,, '6.47 (d, 1H, J = 8.1 Hz), 7.0-7.1 (m, 2H), 7.35 (d, 1H, J = 8.9 Hz) Step Four: 0. 72 g of the boron trifluoride diethyl ether complex were added dropwise to a mixture of 1.28 g of 3-amino-6 -. { 2-c 1 or o-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (me t ox i ca rboni 1) me t oxipi r i di na, 3 ml of 1,2-dimethoxyethane and 1 ml of dichloromethane at -7 ° C. The mixture was stirred for 10 minutes at the same temperature, then 0.31 g of t-butyl nitrite was added to the reaction solution by dripping at -5 ° C or less. The mixture was stirred for 1 hour at the same temperature, then n-pentane was poured into the mixture. The solvent was removed by decantation. 7 ml of ethanol and 1.2 g of zinc (powder) were added to the residue, and this was stirred at reflux temperature for 1.5 hours. The reaction solution was filtered through Celite, and the solvent was distilled off, then the resulting residue was subjected to silica gel chromatography to obtain 0.73 g of 2-. { 2-Chloro-4-fl'uoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -6- (methoxycarbonyl) methoxypyrimidine [compound 2-45 present]. 1H-NR (CDC1./300 MHz) d (ppm): 3.55 (s, 3H), 3.66 (s, 3H), 4.67 (s, 2H), .6.34 (s, 1H), 6.5-6.6 (m, 1H), 7.1-7.2 (m, 1H), 7.3-7.4 (m, 1H), 7.6-7.7 (m, 1H) Production Example 21 Production of compound 7-95 present Step Prime ro Sodium hydride was added to a mixture of 2,6-di-chloro-3-nitroglycine, methyl glycolate and 1,4-dioxane at 10 ° C. The mixture was stirred at room temperature for 2 hours, then, poured into ice water, and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 6-chloro-2- (methoxycarbonyl) methoxy-3-nitropyridine.
Second Step: A mixture of 6-chloro-2- (me toxi carboni 1) me toxi -3-ni tropi idina, platinum oxide and ethanol was stirred for 3 hours at room temperature under a hydrogen atmosphere. The reaction system was purged with nitrogen, then, the reaction solution was filtered through Celite, and the filtrate was concentrated. The residue was subjected to silica gel column chromatography to obtain 3-amino-6-chloro-2- (methoxycarbonyl) methoxypyridine.
Step Three: A diethyl etherate of boron trifluoride was added dropwise to a mixture of 3-amino-6-chloro-2- (methoxy ca rbonyl) methoxypyridine, 1,2-dimethoxyethane and dichloromethane at -10 ° C. After mixing for 10 minutes at the same temperature, a solution of t-butyl nitrite in 1,2-dimethyl t-oxyethane was added to the reaction solution by dripping at -5 ° C or less. After mixing for 30 minutes at the same temperature, n-pentane was poured into the mixture. The lower layer of. The two separated layers were dissolved in acetic anhydride, and the mixture was stirred for 1 hour at 80 ° C. The solvent was removed by distillation, then the resulting residue was subjected to silica gel chromatography to obtain 3 -acetyl-p-chloro-2- (methoxycarbonyl) methoxy iridi a.
Step Four: A mixture of 3-ace t-oxy-6-chloro-2 - (me t-oxy-carboni-1) methoxypropionate, potassium carbonate and methanol was stirred for 3 hours at room temperature. The reaction solution was poured into water, and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 6-chloro-3-hydroxy-2- (methoxycarbonyl) methoxypyridine.
Step Five: To a mixture of 6-chloro-3-hydroxy-2 - (methoxycarbonyl) methoxypyridine, 2, 5-difluoro-4- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1, 2 , 3, 6-tetrahydropyrimidin-1-yl] nitrobenzene and N, N-dimethylformamide were added potassium carbonate, and the mixture was stirred for 2 hours at 70 ° C. The reaction solution was cooled to room temperature, then, poured into ice water, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 3-. { 4-fluoro-5- [3-methyl-2,6-dioxo-4- (t r i fluoromet i 1) -1, 2, 3, 6-tetrahydropyrimidin-1-yl] -2-nitrophenoxy} -β-chloro-2- (methoxycarbonyl) methoxypyridine.
Sixth Step A solution of 3- was added dropwise to a mixture of an iron powder, acetic acid and water. { 4- f luor o- 5- [3 -me t i 1-2, 6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] -2-nitrophenoxy} - 6- chloro -2 - (methoxycarboni 1) met oxyipyridine in acetic acid while maintaining the temperature of the reaction solution at 35 ° C or lower. After the completion of the addition, the mixture was stirred for 2 hours, then, the reaction solution was filtered through Celite, and diluted with ethyl acetate. The mixture was neutralized with saturated aqueous sodium bicarbonate solution, the organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated, then, the resulting residue was subjected to silica gel chromatography to obtain 3 - . { 2-amino-4-f luoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -6-Chloro-2- (methoxycarbon IJmetoxipiri di na.
Step S ep t imo Isoamyl nitrite was added dropwise to a mixture of 3 -. { 2-amino-4-f luor o -5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} 6-chloro-2- (methoxycarbonyl) methoxypyridine, copper (I) chloride, copper (II) chloride and acetonitrile at room temperature, and the mixture was stirred for 1 hour. This reaction solution was poured into 2% hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 3 -. { 2-chloro-4-f luor o -5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -6-chloro-2- (methoxycarboni 1) me toxipi r idina [compound 7-95 present].
Production Example 22 Production of compound 7-109 present First step: Sodium hydride was added to a mixture of 2-chloro-6-me toxi-3-nitropyr idine, methyl glycolate and 1,4-dioxane at 10 ° C. The mixture was stirred at room temperature for 2 hours, then, poured into ice water, and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 6-methoxy-2- (methoxycarbonyl) methoxy-3-nitropyridine.
Second Step: A mixture of 6-methoxy-2- (methoxycarboni 1) met oxy-3-nitropyr idine, platinum oxide and ethanol was stirred for 3 hours at room temperature under a hydrogen atmosphere. The reaction system was purged with nitrogen, then, the reaction solution was filtered through Celite, and the filtrate was concentrated. The residue was subjected to silica gel column chromatography to obtain 3-amino-6-methoxy-2- (methoxycarbonyl) methoxypyridine.
Step Three A diethyl etherate of boron trifluoride was added dropwise to a mixture of 3-amino-6-methoxy-2- (methoxycarbonyl) methoxypyridine, 1,2-dimethoxyethane and dichloromethane at -10 ° C. After mixing for 10 minutes at the same temperature, a solution of t-butyl nitrite in 1,2-dimethoxylate was added dropwise to the reaction solution at -5 ° C or less. After mixing for 30 minutes at the same temperature, n-pentanp was poured into the mixture. The lower layer of the two separate layers was dissolved in acetic anhydride, and the mixture was stirred for 1 hour at 80 ° C. The solvent was distilled off, then, the resulting residue was subjected to silica gel chromatography to obtain 3 -acetoxy-6-methoxy-2- (methoxycarbonyl) methoxypyridine.
Fourth step i «.
- A mixture of 3-ace t-oxy-6-methyl t-oxy- (me t-oxycarboni) toxipi ridine, potassium carbonate and methanol was stirred for 3 hours at room temperature. The reaction solution was poured into water, and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 3-hydroxy-6-met oxy-2 (methoxycarbonyl) methoxypyridine.
Step Five: To a mixture of 3-hydroxy-6-methoxy-2- (methoxycarbonyl) methoxypyridine, 2,5-difluoro-4- [3-methyl] -2,6-dioxo-4- (trifluoromethyl) -1,2, 3, ß-tetrahydropi rimidin-1 -i 1] nor t-benzene and N, N-dimethylformamide was added potassium carbonate, and the mixture was stirred for 2 hours at 70 ° C. The reaction solution was cooled to room temperature, then, poured into ice water, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 3-. { 4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] -2- nor t-rofenoxyl i} - 6 -me t ox i-2 - (methoxycarbonyl) methoxypyridine.
Sixth Step: To a mixture of iron powder, acetic acid and water was added dropwise a solution of 3 -. { 4-f luor o- 5 - [3-met il-2,6-dioxo-4 - (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] -2-nit rofenoxi} - 6-me toxi-2 - (me toxi ca rboni 1) I tox'ipi r idina in acetic acid while maintaining the temperature of the reaction solution at 35 ° C or lower. After the completion of the addition, the mixture was stirred. for 2 hours, then, the reaction solution was filtered through Celite, and diluted with ethyl acetate. The mixture was neutralized with saturated aqueous sodium bicarbonate solution, the organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated, then, the resulting residue was subjected to silica gel chromatography to obtain 3 - . { 2 -ami no-4-f 1 uoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -6-methoxy-2- (methoxycarbonyl) methoxypyridine.
Step Seven Isoamyl nitrite was added dropwise to a mixture of 3 -. { 2-amino-4-f luoro-5 - [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -6-methoxy-2- (me t ox i carboni 1) me t oxip i r i di, copper chloride (I), copper (II) chloride and acetonitrile at room temperature, and the mixture was stirred for 1 hour. This reaction solution was poured into 2% hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 3-. { 2-chloro-4-fluoro-5 - [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,6,6-tetrahydropyrimidin-1-yl] phenoxy} -6-methoxy-2- (me t oxcarboni 1) met oxip i r idine [compound 7-109 present].
Production Example 23 Production of compound 7-8 present A mixture of 0.60 g of 3 -. { 2-c 1 or o-4-fluoro-5- [3-methylene] 2,6-dioxo-4- (tri fluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} - 2 - (methoxycarboni 1) I toxipi ridine [compound 7-7 present], 0.13 g of sodium carbonate and 7.0 ml of ethanol was heated under reflux for 2 hours. This was cooled to room temperature, then, the solvent was distilled off under reduced pressure, and the resulting residue was subjected to silica gel chromatography to obtain 0.55 g of 3 -. { 2-chloro-4-f luoro-5- [3-met i 1 -2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (ethoxycarbonyl) methoxypyridine [compound 7-8 present]. XH-NMR (CDC1./250 MHz) d (ppm): 1.25 (t, 3H, J = 7.1 Hz), 3.50 (q, 3H, J = 1.2 Hz), 4.16 (q, 2H, J = 7.1 Hz) , 4.88 (d, 1H, J = 15.9 Hz), 4.96 (d, 1H, J = 15.9 Hz), 6.29 (s, 1H), 6.9-7.0 (m, 2H), 7.3-7.4 (m, 2H), 7.9-8.0 (m, 1H) Production Example 24: Production of compound 7-48 present A mixture of 0.60 g of 3 -. { 2-cl or o-4-fluoro-5- [3-methyl-1-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (me t oxicarboni 1) I toxipi ridine [compound 7-7 present], 0.13 g of sodium carbonate and 7.0 ml of n-propanol were refluxed for 2 hours. This was cooled to room temperature, then, the solvent was removed by distillation under reduced pressure, and the resulting residue was subjected to silica gel chromatography to obtain 0.62 g d.le 3- (2-chloro-4-f luoro-5- [3 -methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,6,6-tetrahydropyrimidin-1-yl] phenoxy] -2- (n-propoxycarbonyl) methoxypyridine [compound 7-48] ]. 1 H-NMR (CDC1./300 MHz) d (ppm): 0.89 (t, 3H, J = 7.3 Hz), 1.63 (qt, 2H, J = .7.3, 6.5 Hz), 3.50 (q, 3H, J = 0.8 Hz), 4.06 (t, 2H, J = 6.5 Hz), 4.89 (d, 1H, J = 16.0 Hz), 4.97 (d, 1H, J = 16.0 Hz), 6.28 (s, 1H), 6.91 (dd, 1H, J = 7.8, 5.0 Hz), 6.93 (d, 1H, J = 6.5 Hz), 7.31 (dd, 1H, J = 7.8, 1.6 Hz), 7.36 (d, 1H, J = 8.9 Hz) , 7.91 (dd, 1H, J = 5.0, 1.6 Hz) Production Example 25: Production of compound 7-50 present A mixture of 0.30 g of 3 -. { 2-C lor o-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (I t oxi ca rboni 1) I toxipi ri dina [compound 7-7 present], 0.06 g of sodium carbonate and 3.0 ml of n-pentanol was stirred for 1.5 hours at 100 ° C. The reaction solution was cooled to room temperature, then, poured into water, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.07 g of 3-. { 2-Chloro-4-fluoro-5- [3-met i 1-2, 6-di oxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (n-pentyloxycarbonyl) methoxypyridine [compound 7-50 present]. 2 H-NMR (CDC1./300 MHz) d (ppm): 0.88 (t, 3H, J = 6.6 Hz), 1.2-1.4 (m, 4H), 1.5-1.7 (m, 2H), 3.50 (q, 3H, J = 1.0 Hz), 4.0-4.2 (m, 2H), 4.8-5.1 (m, 2H), 6.29 (s, 1H), 6.9-7.0 (m, 2H), 7.28 (dd, 1H, J = 7.9, 1.4 Hz), 7.37 (d, 1H, J = 9.0 Hz), 7.91 ( dd, 1H, J = 4.9, 1.4 Hz) Production Example 7 of the Intermediary: Production of the 3-amino-2- (methoxycarboni 1) me toxipi s idina used in Production Example 13, third process A mixture of 55.9 g of 2- (me toxi carboni 1) Toxi-3-nitroglyphine, 8.64 g of 10% palladium / carbon and 600 ml of ethyl acetate was stirred for 2 hours at room temperature under a hydrogen atmosphere. The reaction system was purged with nitrogen, then, the reaction solution was filtered through Celite, and the filtrate was subjected to silica gel column chromatography to obtain 46.76 g of 3 -ami no -2- (met oxy) ca rboni l) methoxypi ridine.
Production Example 8 of the Intermediary: Production of the 3-acetoxy-2- (methoxycarboni 1) me t oxypyridine used in Production Example 13, fourth process 0. 41 g of trifluoromethanesulfonic acid were added dropwise to a mixture of 0.5 g of 3-ai-2 - (me t oxi ca rbonil) me t oxypi ri di na, 1.5 ml of 1, 2 -dime toxi et anus and 0.5 ml of dichloromethane at -5 ° C. The mixture was stirred for 10 minutes at the same temperature, then, a solution of 0.34 g of t-butyl nitrite in 0.5 ml of 1,2-dimethoxyethoxy was added to the reaction solution dropwise to -5. ° C or less.
The mixture was stirred for 1 hour at the same temperature then, n-pentane was poured into the mixture. The lower layer of the two separated layers was dissolved in 1.5 ml of acetic anhydride, and the mixture was stirred for 30 minutes at 60 ° C. The reaction solution was cooled to room temperature, then, poured into water, and extracted with t-butyl methyl ether. The organic layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated saline solution. Then, it was dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel chromatography to obtain 0.30 g of 3-acetoxy-2- (methoxycarbonyl) methoxypyridine.
Production Example 26 Production of compound 7-17 present Step Prime ro 1. 26 g of hatred hydride were added to a mixture of 5.0 g of 2-chloro-5-n-t and pyridine, 3.13 g of methyl glycolate and 50 ml of tetrahydrofuran at 0 ° C. The mixture was stirred at 0 ° C for 15 minutes, then at room temperature for 1 hour. The reaction solution was poured into ice water, and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 5.18 g of 2- (methoxycarbonyl) methoxy-5-nitropyridine. 1 H-NMR (CDC1./300 MHz) d (ppm): 3.79 (s, 3 H), 5.01 (s, 2 H), 6.99 (d, 1 H, J = 9.1 Hz), 8.41 (dd, 1 H, J = 9.1 , 2.8 Hz), 9.03 (d, 1H, J = 2.8 Hz) Second Step: A mixture of 5.18 g of 2- (methoxycarbonyl) 1 toxi-5-nitropyridine, 0.8 g of 10% palladium / carbon and 50 ml of ethyl acetate was stirred for 3 hours at room temperature under a hydrogen atmosphere. The reaction system was purged with nitrogen, then, the reaction solution was filtered through Celite, and the filtrate was concentrated. The residue was subjected to silica gel column chromatography to obtain 4.45 g of 5-amino-2- (methoxycarbonyl) methoxypyridine. 1 H-NMR (CDC1./250 MHz) d (ppm): 3.3-3.5 (bs, 2H), 3.76 (s, 3H), 4.82 (s, 2H), 6.72 (d, 1H, J = 8.6 hz), 7.04 (dd, 1H, J = 8.6, 2.9 Hz), 7.58 (dd, 1H, J = 2.9 'Hz) P se Third 1. 46 ml of trifluoromethanesulfonic acid was added dropwise to a mixture of 3.0 g of 5-amino-2 - (me t ox i ca rboni 1) me t oxypyridine, 9 ml of 1, 2 -dime toxi et ano and 3 ml of dichloromethane at -10 ° C. The mixture was stirred for 10 minutes at the same temperature, then, to the reaction solution, a solution of 2.35 ml of t-butyl nitrite in 1 ml of 1,2-dimethoxyethane was added to the mixture, and stirred. for 20 minutes at the same temperature, then, n-pentane was poured into the mixture. The precipitated solid was washed with n-pentane, then dissolved in 18 ml of acetic anhydride, and the mixture was stirred for 2 hours at 80 ° C. The mixture was poured into ice water, and extracted with t-butyl methyl ether. The organic layer was concentrated, then diluted with t-butyl methyl ether. The diluted was washed with saturated aqueous sodium bicarbonate solution, then saturated saline solution, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 1.4 g of 5-acetoxy-2- (methoxy ca rboni 19 methoxypyridine. 1 H-NMR (CDC1./300 MHz) d (ppm): 2.30 (s) , 3H), 3.77 (s, 3H), 4.89 (s, 2H), 6.88 (d, 1H, J = 8.8 Hz), 7.40 (dd, 1H, J = 8.8, 2.8 Hz), 7.89 (dd, 1H, J = 2.8 Hz) Step Cua rto: A mixture of 1.4 g of 5-acetoxy-2- (methoxycarbonyl) I toxipi ridine, 0.47 g of potassium carbonate and 10 ml of methanol was stirred for 4.5 hours at room temperature. The solvent was distilled off under reduced pressure, and to the resulting residue water was added, then neutralized with hydrochloric acid. The mixture was extracted with ethyl acetate, and the organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 1.0 g of 5-hydroxy-2- (methoxycarbonyl) methoxypyridine. X H-NMR (CDCl 3/300 MHz) d (ppm): 3.78 (s, 3 H), 4.84 (s, 2 H), 5/92 (bs, 1 H), 6.72 (d, 1 H, J = 8.9 Hz), 7.12 (dd, 1H, J = 8.9, 2.9 Hz), 7.62 (d, 1H, J = 2.9 Hz) Fifth Step To a mixture of 0.5 g of 5-hydroxy-2- (me t ox i carboni 1) me t ox ipi ri dina, 0.80 g of 2,5-difluoro-4- [3-methyl-2,6-dioxo- 4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-li 1] nor t-benzene and 5 ml of N, N-dimet i If ormamide was added 0.35 g of potassium carbonate, and the mixture was stirred for 1.5 hours at 50 ° C. The solution was cooled to room temperature, poured into a mixture of water, hydrochloric acid and saline, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.93 g of 5 -. { 4-f luor o -5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] -2-nitrophenoxy} -2 - (methoxycarbonyl) methoxypyridine. 1 H-NMR (CDCl 3/300 MHz) d (ppm): 3.54 (q, 3 H, J = 1.2 Hz), 3 ,. 79 (s, 3H), 4.89 (s, 2H), 6.34 (s, 1H), 6.8-7.0 (m, 2H), 7.42 (dd, 1H, J = 9.2, 2.9 Hz), 7.88 (d, 1H, J = 8.5 Hz), 7.96 (d, 1H, J = 2.9 Hz) Sixth Step To a mixed solution of 1.2 g of an iron powder, 5 ml of acetic acid and 0.5 ml of water was added dropwise a solution of 0.93 g of 5 -. { 4-f 1 -or o -5- [3 -me t i 1-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] -2-nitrophenoxy} - 2 - (me t ox i ca rboni 1) me t oxyp i imidine in 4 ml of acetic acid while maintaining the temperature of the reaction solution at 35 ° C or lower. After the completion of the addition, the mixture was stirred for 2 hours, then, filtered through Celite, and concentrated. The residue was diluted with water, and extracted with ethyl acetate. The organic layer was mixed, washed with saturated aqueous sodium bicarbonate solution, then saturated saline, dried over anhydrous magnesium sulfate, and concentrated. Then, the resulting residue was subjected to silica gel chromatography to obtain 0.83 g of 5 -. { 2 -ami no- 4-f luor or -5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,6,6-tetrahydropyrimidin-1-yl] phenoxy} - 2 - (methoxycarbonyl) methoxypyridine. 1 H-NMR (CDC1./250 MHz) d (ppm): 3.52 (q, 3 H, J = 1.2 Hz), 3.78 (s, 3 H), 4.16 (bs, 2 H), 4.87 (s, 2 H), 6.31 fs , 1H), 6.57 (d, 1H, J = 6.8 Hz), 6.64 (d, 1H, J = 10.8 Hz), 6.85 (dd, 1H, J = 8.9, 0.5 Hz), 7.35 (dd, 1H, J = 8.9, 3.1 Hz), 7.90 (dd, 1H, J = 3.1, 0.5 Hz) Step S ep t imo 0. 3 g of isoamyl nitrite were added dropwise to a mixture of 0.83 g of 5-. { 2-amino-4-fluoro-5- [3-met-il-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (methoxycarbonyl) methoxypyridine, 0.34 g of copper (I) chloride, 0.69 g of copper (II) chloride and 3 ml of acetonitrile at room temperature, and the mixture was stirred for 1 hour. 0.3 g of isoamyl nitrite were added to the mixture, and it was stirred for 20 minutes. This reaction solution was poured into 2% hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.52 g of 5 -. { 2-C-Parroro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} - 2 - (me toxi ca rboni 1) me t oxipi r idina [compound 7-17 present]. XH-NMR (CDC1./250 MHz) d (ppm): 3.53 (q, 3H, J = 1.3 Hz), 3.78 (s, 3H), 4.88 (s, 2H), 6.33 (s, 1H), 6.76 ( d, 1H, J = 6.5 Hz), 6.88 (d, 1H, J = 8.9 Hz), 7.3-7.4 (m, 1H), 7.39 (d, 1H, J = 8.9 Hz), 7.8-7.9 (m, 1H ) Production Example 27 Production of compound 7-12 present Step P r ime ro A mixture of 0.08 g of 5-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (methoxycarboni 1) I toxipi ridine [compound 7-17 present] and 1 ml of 48% hydrobromic acid was stirred at reflux temperature for 3 hours. The mixture was neutralized with saturated aqueous sodium bicarbonate solution, and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and concentrated to obtain O.Oβ g of 5 -. { 2-cl or o-4-f luoro-5 - [3-methyl-2, b-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2-pyridone. XH-NMR (CDC1./300 MHz) d (ppm): 3.51 (s, 3H), 6.31 (s, 1H), 6.58 (d, 1H, J = 9.8 Hz), 6.79 (d, 1H, J = 6.5 Hz), 7.24 (d, 1H, J = 3.0 Hz), 7.3-7.4 (m, 2H) Second Step: To a mixture of 60 mg of 5 -. { 2-cl gold-4-f luoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2-pyridone, 1.0 ml of tetrahydrofuran, 25 mg of methyl lactate, and 64 mg of triphenylphosphine, 123 mg of a 40% solution of diisopropyl azodicarboxylate in toluene, and the mixture was stirred for 2 hours at room temperature. The reaction solution was poured into water, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 20 mg of 5-. { 2-chloro-4-fluoro-5- [3-meth i 1-2, 6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- . { 1- (methoxycarbonyl) ethoxy (pyridine [compound 7-12 present]. 1 H-NMR (CDC1./300 MHz) d (ppm): 1.60 (d, 3H, J = 7.0 Hz), 3.53 (s, 3H), 3.75 (s, 3H), 5.28 (q, 1H, J = 7.0 Hz), 6.32 (s, 1 / 2H), 6.33 (s, 1 / 2H), 6.7-6.8 (m, 1H), 6.84 (d, 1H, J = 9.1 Hz), 7.3-7.4 (m, 1H), 7.38 (d, 1H, J = 8.8 Hz), 7.8-7.9 (m, 1H) Production Example Production of compound 1-45 present Step One: 0.4 g of sodium hydride were added to a mixture of 1.59 g of 4-chlor or 6-methoxy-2-methylthiopyrimidine, 0.98 g of methyl glycolate and 10 ml of N, -dimet and 1-formamide. 0 ° C. The mixture was stirred at room temperature for 5 hours, then, the reaction solution was poured into water, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 1.22 g of 6-methoxy-4- (methoxycarbonyl) methoxy-2-methylthiopyrimidine. ^ -NMR (CDC1./250 MHz) d (ppm): 2.48 (s, 3H), 3.77 (s, 3H), 3.93 (s, 3H), 4.88 (s, 2H), 5.87 (s, 1H) Second Step: 2. 59 g of 3-chloroperoxybenzoic acid were added to a solution of 1.22 g of 6-methoxy-4- (methoxy-carbonyl) methoxy-2-methylthiopyrimidine in 10 ml of chloroform at 0 ° C. The mixture was stirred at room temperature for 3 hours, then 30 ml of saturated aqueous sodium thiosulfate solution was added to the mixture. The mixture was poured into saturated aqueous sodium bicarbonate solution, extracted with chloroform, the organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated, then, the resulting residue was subjected to silica gel to obtain 1.32 g of 6-methoxy-4- (methoxycarbonyl) methoxy-2-methylsulfonylpyrimidine. X H-NMR (CDCl 3/300 MHz) d (ppm): 3.26 (s, 3 H), 3.78 (s, 3 H), 4.06 (s, 3 H), 4.97 (s, 2 H), 6.34 (s, 1 H) Step Three To a mixture of 400 mg of 2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1, 2, 3, 6-tetrahydrohydrate imidin-1-yl ] phenol, 359 mg of 6-methoxy-4- (methoxycarbonyl) methoxy-2-mti-1-sulphonylimide and 3 ml of N, N-dimethylformamide, 196 mg of potassium carbonate was added, and the mixture it was stirred for 1 hour at 80 ° C. The reaction solution was cooled to room temperature, then, this reaction solution was poured into water, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 620 mg of 2 -. { 2-C lor o-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -6-methoxy-4- (methoxycarbonyl) methoxypyrimidine [compound 1-45 present]. XH-NMR (CDC1./300 MHz) d (ppm); 3.55 (s, 3H), 3.71 (s, 3H), 3.87 (s, 3H), 4.7 £ (s, 2H), 5.95 (s, 1H), 6.34 (s, 1H), 7.1-7.2 (m, 1H) ), 7.37 (d, 1H, J = 9.1 Hz) Melting point: 60.3 ° C Production Example 29 Produces ion of compound 1-42 present Step Prime r o 3. 86 g of methanol solution of 28% sodium methoxide were added dropwise over 20 minutes to a solution of 3.9 g of 4,6-dichloro-2-met ilt-iopyrimidine in 20 ml of N, N-dimethylformamide at 0 ° C. . Then the mixture was stirred at room temperature for 7 hours, 20 g of ice was added to the mixture, then the white precipitate was collected by suction filtration, and the solid / washed with water. The solid was dissolved in ethyl acetate, washed with saturated saline solution, dried over anhydrous magnesium sulfate, and concentrated to obtain 3.18 g of 4-chloro- or 6-me t-oxy-methyl-11-pyridine. na X H-NMR (CDCl 3/300 MHz) d (ppm): 2.55 (s, 3 H), 3.98 (s, 3 H), 6.41 (s, 1 H) Second Step: 0. 4 g of sodium hydride were added to a mixture of 1.59 g of 4-c 1 or ro-6-methyl-oxy-2-methylthiopyrimidine, 1.13 g of methyl lactate and 10 ml of N, N-dimetho 1 formamide at 0 ° C. The mixture was stirred at room temperature for 5 hours, then, the reaction solution was poured into water, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 1.5 g of 6-methoxy-4- (1- (methoxycarbonyl) ethoxy) -2-methylthiopyrimidine. XH-NMR (CDC1./250 MHz) d (ppm): 1.58 (d, 3H, J = 7.0 Hz), 2.46 (s, 3H), 3.73 (s, 3H), 3.92 (s, 3H), 5.33 ( , q_, 1H, J = 7.0 Hz), 5.83 (s, 1H) Step Three 2. 81 g of 3-chloroperoxybenzoic acid were added to a solution of 1.40 g of 6-methoxy-4-. { 1- (methoxycarbonyl) ethoxy} - 2-methylthiopyrimidine in 13 ml of chloroform at 0 ° C. The mixture was stirred at room temperature for 3 hours, then 30 ml of saturated aqueous sodium thiosulfate solution was added to the mixture. The mixture was poured into saturated aqueous sodium bicarbonate solution, extracted with chloroform, the organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated, then, the resulting residue was subjected to silica gel to obtain 1.62 g of 6-methoxy-4-. { 1- (methoxycarbonyl) ethoxy} -2-methyl-sulfonylpyrimidine. XH-NMR (CDC1./250 MHz) d (ppm): 1.63 (d, 3H, J = 7.0 Hz), 3.25 (s, 3H), 3.75 (s, 3H), 4.06 (s, 3H), 5.36 ( q, 1H, J = 7.0-Hz), 6.30 (s, 1H) Fourth Step To a mixture of 400 mg of 2-chloro-4-fluoro-5- [3-methyl 1-2, ß-dioxo-4- (trifluoromethyl) -1, 2, 3, 6- tet rahidropir imidin- 1 -i 1] phenol, 377 mg of 6-methoxy-4-. { 1- (methoxycarbonyl) ethoxy} After adding 1 ml of its 1 pyrimidine and 3 ml of N, N-dimethylformamide, 196 mg of potassium carbonate was added, and the mixture was stirred for 1 hour at 80 ° C. The reaction solution was cooled to room temperature, then, this reaction solution was poured into water, and extracted with ethyl acetate. The organic layer was washed with saturated saline solution, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 630 mg of 2- (2-c lor o-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1. , 2, 3, 6-tetrahydropyrimidin-1-yl] fehoxyl] - ß-methoxy-4-. {L- (methoxycarbonyl) ethoxy} pyrimidine [compound 1-42 present]. XH-NMR (CDCl 3 / 300 MHz) d (ppm): 1.52 (d, 3H, J = 6.8 Hz), 3.55 (s, 3H), 3.67 (s, 3H), 3.87 (s, 3H), 5.2-573 (m, 1H) , 5.91 (s, 1H), 6.35 (s, 1H), 7.16 (d, 1H, J = 6.7 Hz), 7.37 (d, 1H, J = 9.1 Hz) Melting point: 71.2 ° C Production Example 30 Production of compound 7-82 present A mixture of 0.60 g of 3 -. { 2-C lor o-4-fluoro-5- [3-met i 1-2, 6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2 - (I tox i carboni 1) I toxipi ridine [compound 7-7 present], 0.13 g of sodium carbonate, 0.39 g of benzyl alcohol and 2.4 ml of toluene was heated at 90 ° C for 2 hours, then low reflux for 2 hours. This was cooled to room temperature, then, the solvent was distilled off under reduced pressure, and the resulting residue was subjected to silica gel chromatography to obtain 0.24 g of 3 -. { 2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3, β-tetrahydropyrimidin-1-yl] phenoxy} -2- (benzyloxy carboni 1) met oxypyr idine [compound 7-82 present]. X H-NMR (CDCl 3/300 MHz) d (ppm): 3.47 (s, 3 H), 5.15 (s, 2 H), '6.25 (s, 1 H), 6.8-7.0 (m, 2 H), 7.2-7.4 (m , 7H), 7.89 (dd, 1H, J = 4.9, 1.3 Hz) Production Example 31 Production of compound 7-6 present A mixture of 0.24 g of 3 -. { 2-c 1 or o-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (benzylox i ca rbon i 1) me t ox ip ir idine [compound 7-82 present], 10 mg of palladium / 10% carbon and 1 ml of ethyl acetate was stirred for 1.5 hours at room temperature under a hydrogen atmosphere. The reaction system was purged with nitrogen, then, the reaction solution was filtered through Celite, and the filtrate was concentrated. The residue was subjected to silica gel column chromatography to obtain 0.16 g of 3-. { 2-Chloro-4-f-luoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydro-rimidin-1-yl] phenoxy} -2-carboxytoxhoxidine [compound 7-6 present]. 1 H-NMR (CDCl 3/300 MHz) d (ppm): 3.50 (s, 3H), 4.92 (s, 2H), 6.32 (s, 1H), 6.80 (d, 1H, J = 6.4 Hz), 6.95 (dd, / 1H, J = 7.7, 4.9 Hz), 7.35 (dd, 1H, J = 7.7, 1.2 Hz), 7.37 (d, 1H, J = 6.0 Hz), 7.93 (dd, 1H, J = 4.9, 1.2 Hz) Production Example 32: Production of compound 7-84 present 0. 13 g of l- [3- (dimethylamino) propyl] -3-ethylcarbodiimide hydrochloride was added to a mixture of 0.30 g of 3-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} - 2 -carboximet oxipi ridine [compound 7-6 present], 56 mg of O-me ti hydrochloride iodine oxyamy, 68 mg of triethylamine and 2 ml of N, N-dimyl 1 formamide at room temperature, and it was stirred for 2 hours. The mixture was then poured into water and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 90 mg of 3 -. { 2-chloro-4-f luor o- 5 - [3 -me t i 1-2, ß-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} - 2 - [(me toxi aminocarboni 1) me tox] p i ridine [compound 7-84 present]. X H-NMR (CDCl 3/300 MHz) d (ppm): 3.52 (s, 3 H), 3.74 (s, 3 H), 4.87 (s, 2 H), 6.32 (s, 1 H), 6.71 (d, 1 H, J = 6.0 Hz), 6.99 (dd, 1H, J = 7.6, 5.0 Hz), 7.38 (dd, 1H, J = 7.6, 1.7 Hz), 7.44 (d, 1H, J = 8.7 Hz), 8.00 (dd, 1H, J = 5.0, 1.7 Hz), 8.7-9.0 (bs, 1H) Production Example 33: Production of compound 7-119 present 0. 13 g of l- [3- (dimethylamino) propyl] -3-ethylcarbodiimide hydrochloride were added to a mixture of 0.30 g of 3-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2-carboxyme t oxypyr idine [compound 7-6 present], 60 mg of methyl glycolate and 2 ml of N, N-dime t 1 formamide at room temperature, and stirred for 1.5 hours. The mixture was then poured into water and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.18 g of 3 -. { 2-C lor o-4-fluoro-5- [3-methyl-2, €? -dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- [(methoxycarbonyl) methoxycarbonylmethoxy] pyridine [compound 7-119 present]. XH-NMR (CDC1./300 MHz) d (ppm): 3.50 (s, 3H), 3.74 (s, 3H), 4.65 (s, 2H), 5.01 (d, 1H, J = 16.2 Hz), 5.09 ( d, 1H, J = 16.2 Hz), 6.28 (s, 1H), 6.88 (d, 1H, J = 6.7 Hz), 6.93 (dd, 1H, J = 7.8, 4.9 Hz), 7.32 (dd, 1H, J = 7.8, 1.4 Hz), 7.37 (d, 1H, J = 9.0 Hz), 7.93 (dd, 1H, J = 4.9, 1.4 Hz) Production Example 34 Production of compound 7-118 present 0. 13 g of l- [3- (dimethylamino) propyl] -3-ethylcarbodiimide hydrochloride were added to a mixture of 0.30 g of 3-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2-carboxyme toxipi ridine [compound 7-6 present], 49 mg of acetone oxime and 2 ml of, N-dimethyl-l-ormamide at room temperature, and stirred for 2 hours. The mixture was then poured into water and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.16 g of 3 -. { 2-chloro-4-f luoro-5 - [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} - 2 -i s opropi lidenami noca rbon i lme toxipi ridina [compound 7-118 present]. 1 H-NMR (CDCl 3/300 MHz) d (ppm): 1.94 (s, 3 H), 2.01 (s, 3 H), 3.94 (s, 3 H), 5.0-5.2 (m, 2 H), 6.27 (s, 1 H) , 6.92 (dd, 1H, J = 7.8, 4.9 Hz), 6.98 (d, 1H, J = 6.5 Hz), 7.3-7.4 (m, 2H), 7.92 (d, 1H, J = 4.9 Hz) Production Example 35: Production of compound 9-7 present A solution of 0.5 g of 3 -. { 2 -ami non-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (methoxycarbonyl) methoxypyridine in 1. 5 ml of acetonitrile was added to a mixture of 0.22 g of copper (I) bromide, 0.05 g of copper (II) bromide and 1 ml of acetonitrile at 0 °. C. A solution of 0.18 g of t-butyl nitrite in 1 ml of acetonitrile was added to the mixture by dripping for 30 minutes, then stirred at room temperature for 1 night. This reaction solution was poured into hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.28 g of 3-. { 2-bromo-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (methoxycarbonyl) methoxypyridine [compound 9-7 present]. 1 H-NMR (CDCl 3/300 MHz) d (ppm): 3.50 (q, 3 H, J = 1.2 Hz), 3.70 (s, 3 H), 4.8-5.0 (m, 2 H), 6.29 (s, 1 H), 6.88 (d, 1H, J = 6.4 Hz), 6.93 (dd, 1H, J = 7.8, 5.0 Hz), 7.32 (d, 1H, J = 7.8 Hz), 7.53 (d, 1H, J = 8.5 Hz), 7.92 (d, 1H, J = 5.0 Hz) Production Example 36 Production of compound 9-27 present A mixture of 0.23 g of 3 -. { 2-bromo-4-fluoro-5- [3-methyl-2, β-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (met ox i carboni 1) methoxypi ridine [compound 9-7 present], 75 mg of copper cyanide and 2 ml of N-me t -yl-2-pyrrolidone was stirred at 160 ° C for 2 hours. The reaction mixture was cooled to room temperature, water was added to the mixture and the resultant was extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.16 g of • 3 -. { 2-cyano-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2 - (me t ox i ca rbon i 1) me t ox ip i r i di na [compound 9-27 present]. Melting point: 173.1 ° C 1 H-NMR (CDCl 3/300 MHz) d (ppm): 3.49 (s, 3 H), 3.67 (s, 3 H), 4.8-5.0 (m, 2 H), 6.28 (s, 1 H) , 6.96 (d, 1H, J = 5.7 Hz), 7.00 (d, 1H, J = 7.8, 5.0 Hz), 7.50 (d, 1H, J = 8.4 Hz), 7.54 (d, 1H, J = 7.8 Hz) , 8.01 (d, 1H, J = 5.0 Hz) Production Example 37: Production of compound 2-42 present First step: 2. 0 g of sodium hydride were added to a mixture of 9.65 g of 2,6-di-chloro-3-nitropyridine, 5.41 g of benzyl alcohol and 30 ml of tetrahydrofuran at 0 ° C. The mixture was stirred at 0 ° C for 1.5 hours, then at room temperature for 1.5 hours. The reaction solution was poured into ice water, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 10.93 g of 6-chloro-2-benzyl 1 ox i -3 -n i t rop i r idine. 1 H-NMR (CDCl 3/250 MHz) d (ppm): 5.18 (s, 2 H), 7.05 (d, 1 H, J = 8.3 Hz), 7.3-7.6 (m, 5 H), 8.28 (d, 1 H, J = 8.3 Hz) Step Second A mixture of 5.29 g of 6-chloro-2-benzyloxy-3-nitropyridine, 6.77 g of 2-chloro-4-fluoro-5- [3-methyl-2, d-dioxo-4- (trifluoromethyl) -1, 2,3,6-tetrahydropi imidin-1-yl] phenol, 3.32 g of potassium carbonate and 30. ml of N, N-dimet and formamide was stirred for 30 minutes at room temperature, then at 50 ° C for 2.5 hours. The resulting residue was added to ice water, extracted with ethyl acetate, and the organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was recrystallized from ethyl acetate and hexane to obtain 9.11 g of 6 -. { 2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2-benzyloxy-3-nitropyridine. 1 H-NMR (CDC1./300 MHz) d (ppm): 3.56 (s, 3H), 5.29 (s, 2H), 6.37 (s, 1H), 6.68 (d, 1H, J = 8.6 Hz), 7.1-7.4 (m, 6H), 7.37 (d, 1H, J = 8.8 Hz), 8.47 (d, 1H, J = 8.6 hz) Step Three: To a mixed solution of 3.0 g of an iron powder, 15 ml of acetic acid and 1.5 ml of water was added dropwise a solution of 3. 0 g of 6-. { 2-cl or o- 4-f luoro-5 - [3 -me t i 1 -2,6-dioxo-4- (trifluoromethyl) -1,2,6,6-tetrahydropyrimidin-1-yl] phenoxy} -2-benzyloxy-3-ni t-pyrythrin in 10 ml of acetic acid and 10 ml of ethyl acetate while maintaining the temperature of the reaction solution at 35 ° C or lower. After completion of the addition, the mixture was stirred overnight, then, the reaction solution was filtered through Celite, and the solvent was removed under reduced pressure. The residue was diluted with saturated aqueous sodium bicarbonate solution, extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The resulting residue was subjected to silica gel chromatography to obtain 2.55 g of 3-ami no- 6 -. { 2-c lo o- 4-f luor o- 5 - [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2-benzyloxypyridine XH-NMR (CDCÍ3 / 30Ó MHz) d (ppm): 3.51 (s, 3H), 3.60 (bs, 2H), 5.1-5.3 (m, 2H), 6.33 (s, 1H), 6.42 8d, 1H, J = 7.9 Hz), 6.99 (d, 1H, J = 8. 2 Hz), 7.08 (d, 1H, J = 6.7 Hz), 7.2-7.4 (m, 6H) Fourth Step 1. 38 g of diethyl ether complex of boron trifluoride were added dropwise to a mixture of 2.55 g of 3-ami no- 6 -. { 2-c 1 or o -4-fluoro-5- [3-met i 1-2, 6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2-benzilox ipir idine, 6 ml of 1,2-dimethoxyethane and 2 ml of dichloromethane at -5 ° C. The mixture was stirred for 15 minutes at the same temperature, then 0.59 g of t-butyl nitrite at -5 ° C were added to the reaction solution. The mixture was stirred for 1 hour at the same temperature, then n-pentane was poured into the mixture. The solvent was removed by decantation. 15 ml of ethanol, and 2.3 g of zinc (powder) were added to the residue, and stirred at reflux temperature for 1.5 hours. The reaction solution was filtered through Celite. and the solvent was distilled off, then the resulting residue was subjected to silica gel chromatography to obtain 0.75 g of 2 -. { 2-chloro-4-f luor o -5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -ß-benc i loxipi ridina. XH-NMR (CDC1./300 MHz) d (ppm): 3.52 (s, 3H), 5.0-5.2 (m, 2H), 6.34 (s, 1H), 6.5-6.6 (m, 2H), 7.1-7.4 (m, 6H), 7.34 (d, 1H, J = 9.1 hz), 7.5-7.7 (m, 1H) Fifth Step A mixture of 0.90 g of 2 -. { 2-C-Parroro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluor otne t i 1) - 1, 2, 3, 6-tetrahydropyrimidin-1-yl] phenoxy} - 6-benzyl oxypyridine, 0.1 g of palladium / carbon at 10% and 5 ml of ethyl acetate was stirred for 3 hours at room temperature under hydrogen atmosphere. The reaction system was purged with nitrogen, then, the reaction solution was filtered through Celite, and the filtrate was concentrated. The residue was subjected to silica gel column chromatography to obtain 0.60 g of 6-. { 2-chloro-4-fluoro-5- [3-me t i 1 -2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2-pyridone. X H-NMR (CDCl 3/250 MHz) d (ppm): 3.54 (s, 3 H), 6.11 (d, 1 H, J = 7.9 Hz), 6.33 (s, 1 H), 6.44 (d, 1 H, J = 7.8 Hz ), 7.09 (d, 1H, J = 6.7 Hz), 7.37 (d, 1H, J = 8.9 Hz), 7.55 (dd, 1H, J = 7.9, 7.8 Hz) Sixth Step: To a mixture of 50 mg of 6 -. { 2-C-Parroro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2-pyridone, 21 mg of methyl 2-bromoprone opi ona and 1 ml of N, N-dime t 1 formamide were added 21 mg of potassium carbonate, and the mixture was stirred for 1 hour at 50 ° C. The solution was cooled to room temperature, poured into water, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 72 mg of 2-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -6-. { 1- (methoxycarbonyl) ethoxy} pyridine [compound 2-42 present]. xH-NM (CDC1./300 MHz) d (ppm): 1.48 (d, 3H, J = 6.9 Hz), 3.55 (s, 3H), 3.60 (s, 3 / 2H), 3.61 (s, 3 / 2H), 5.10 (q, 1H, J = 6.9 Hz), 5.12 (q, 1H, J = 6.9 Hz) / 6.34 (s, 1H), 6.55 (d, 1H, J = 0 Hz) 6.56 (dd 1H J = 7 2.9 Hz 7. 14 (dd, 1H, J = 6.9, 2.9 Hz), 7.37 (d, 1H, J = 9.0 Hz), 7.62 (dd, 1H, J = 7.9, 6.9 Hz) Production Example 38: Production of compound 1-67 present To a mixture of 400 mg of 2-chloro-4-fluoro-5- [3-methyl-2, β-dioxo-4- (trifluoromethyl) - 1, 2, 3, 6- tetr ah i dr op ir imi di n - 1 - il] an i 1 ina, 360 mg of - 6 -me t ox i - 4 - (me t oxi carbon i 1) mt ox i -2 -me ti 1 s ul foni lp imi dina y 2 ml of N, N-dimethylformamide, 196 mg of potassium carbonate was added, and the mixture was stirred for 5 hours at 80 ° C. The reaction solution was cooled to room temperature, then, this reaction solution was poured into water, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 98 mg of 2 -. { 2-c 1 gold-4-fluoro-5- [3-methyl-1-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenylamino} -6-methoxy-4- (methoxycarbonyl) methoxypyrimidine [compound 1-67 present]. XH-NR (CDCl3 / 250 MHz) d (ppm): 3.57 (s, 3H), 3.65 (s, 3H), 3.91 (s, 3H), 4.7-4.9 (m, 2H), 5.75 (s, 1H ), 6.38 (s, 1H), 7.32 (d, 1H, J = 8.8 Hz), 7.37 (bs, 1H), 8.37 (d, 1H, J = 7.3 Hz) Melting point: 155.6 ° C Production Example 39 Produces ion of compound 2-52 present A mixture of 1 g of 3-amino-2 -. { 2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3, β-tetrahydropyrimidin-1-y1] phenoxy} pi r idi and 1.16 g of methyl 2-methylpropionate were stirred for 30 minutes at 60 ° C, then for 4 hours at 80 ° C. The mixture was subjected to silica gel column chromatography to obtain 0.4 g of 2 -. { 2-c 1 or o- 4-f luor o- 5 - [3 -me t i 1 -2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -3- . { 1- (methoxycarbonyl) et ilamino} pyridine [compound 2-52 present e]. Melting point: 66.4 ° C Production Example 40 Production of compound 7-8 present Step Prime ro llg of sodium hydride were added to a mixture of 39.63 g of 2-chloro-3-nitropyridine, 31.23 g of ethyl glycolate, 250 ml of tetrahydrofuran and 20 ml of N, N-dimethylformamide at 0 ° C. The mixture was stirred at room temperature for 5 hours, then, the reaction solution was poured into ice water, and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 48.3 g of 2- (and oxycarboni 1) met oxy-3-n-tropi-ridine. 1 H-NMR (CDCl 3/300 MHz) d (ppm): 1.26 (t, 3 H, J = 7.1 Hz), 4.23 (q, 2 H, J = 7.1 Hz), 5.06 (s, 2 H), 7.0-7.2 ( m, 1H), 8.3-8.4 (m, 2H) Second Step: A mixture of 48.3 g of 2- (et oxi ca rbon i 1) methoxy-3-nitroglyph, 7.8 g of 10% palladium / carbon and 540 ml of ethyl acetate was stirred for 3 hours. hours at room temperature under a hydrogen atmosphere. The reaction system was purged with nitrogen, then, the reaction solution was filtered through Celite, and the filtrate was concentrated. The residue was subjected to silica gel column chromatography to obtain 37.1 g of 3-amino-2- (e toxi carbonyl) met oxy pyridine. XH-NMR (CDCl3 / 300 MHz) d (ppm): 1.27 (t, 3H, J = 7.1 Hz), 3.8-3.9 (b, 2H), 4.24 (q, 2H, J = 7.1 Hz), 4.93 (s) , 2H), 6.7-6.8 (m, 1H), 6.8-7.0 (m, 1H), 7.4-7.6 (m, 1H) Step Three 70 9. 18 g of trifluoromethanesulfonic acid were added dropwise to a mixture of 12 g of 3-amino-2- (ethoxycarbonyl) met oxy pyridine, 36 ml of 1,2-dimethoxyethane and 12 ml of dichloromethane at -5 ° C. The mixture was stirred for 10 minutes at the same temperature, then, to the reaction solution, a solution of 7.57 g of t-butyl nitrite in 3 ml of 1,2-dimethoxyethane a-5 was added dropwise. ° C or lower. The mixture was stirred for 30 minutes at the same temperature, then n-pentane was poured into the mixture. The lower layer of the two separate layers was dissolved in 12 ml of acetic anhydride, and the mixture was stirred for 2.5 hours at 50 ° C. The reaction solution was poured into ice water, and extracted with t-butyl methyl ether. The organic layer was washed with saturated aqueous sodium bicarbonate solution, then saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The resulting residue was subjected to silica gel chromatography to obtain 4.2 g of 3-acetoxy-2- (e toxica rboni 1) methoxypyridine. XH-NMR (CDC1./300 MHz) d (ppm): 1.26 (t, 3H, J = 7.1 Hz), 2.34 (s, 3H), 4.22 (q, 2H, J = 1 7. 1 Hz), 4.90 (s, 2H), 6.94 (dd, 1H, J = 7.8, 5.0 Hz), 7.38 (dd, 1H, J = 7.8, 1.5 Hz), 7.97 (dd, 1H, J = 5.0, 1.5 Hz) Step Four: A mixture of 13.8 g of 3-acetoxy-2- (ethoxy ca rboni 1) me t ox ip i rdinin, 4.38 g of potassium carbonate and 60 ml of ethanol was stirred overnight at room temperature. The reaction solution was poured into a mixture of water, sodium chloride and hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 10.45 g of 3-hydroxy-2- (ethoxycarbonyl) methoxypyridine. XH-NMR (CDCl3 / 250 MHz) d (ppm): 1.28 (t, 3H, J = 7.1 Hz), 4.25 (q, 2H, J = 7.1 Hz), 4.97 (s, 2H), 5.93 (s, 1H ), 6.86 (dd, 1H, J = 7.7, 4.9 Hz), 7.17 (dd, 1H, J = 7.7, 1.6 Hz), 7.65 (dd, 1H, J = 4.9, 1.6 Hz) Step Five: To a mixture of 10.45 g of 3-hydroxy-2- (ethoxy carboni 1) met oxypyridine, 16.92 g of 2,5-diluoro-4- [3-methyl-2,6-dioxo-4- (trifluoromethyl) - 1, 2, 3, 6-tetrahydropyrimidin-1-yl] nitrobenzene and 100 ml of N, N-dimethylformamide were added 7.32 g of potassium carbonate, and the mixture was stirred for 2 hours at 70 ° C. The solution was cooled to room temperature, poured into a mixture of ice water, sodium chloride and hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with saturated saline solution, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to UTOna colony chromatography on silica gel to obtain 17.28 g of 3 -. { 4 - f luor o- 5 - [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] -2-nitrophenoxy) -2 - (ethoxy) rbon i 1) me t ox ip irid ina [compound 9-46 present]. ^ -NMR (CDC1./300 MHz) d (ppm): 1.25 (t, 3H, J = 7.3 Hz), 3.50 (s, 3H), 4.12 (q, 2H, J = 7.3 Hz), 4.85 (d, 1H, J = 15.9 Hz), 4.95 (d, 1H, J = 15.9 H) , 6.28 (s, 1H), 6.98. (dd, 1H, J = 7 5.0 Hz), 7.13 (d, 1H, J = 6.1 Hz), 7.50 (dd, 1H, J = 7.8, 1.4 Hz), 7.87 (d, 1H, J = 8.6 Hz), 7.99 (dd, 1H, J = 5.0, 1.4 Hz) Sixth Step: To a mixture of 17 g of an iron powder, 30 ml of acetic acid and 3 ml of water was added dropwise a solution of 17.28 g of 3- (4-f luoro-5- [3-methyl-2, β] -dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] -2-nitrophenoxy} -2- (and oxy-carbon i) me t-oxypyldine [compound 9-46] present] in 20 ml of acetic acid while maintaining the temperature of the reaction solution at 35 ° C or lower.After completion of the addition, the mixture was stirred for 1 hour at room temperature, for 3 hours at 40 ° C. C, then, the reaction solution was filtered through Celite, and diluted with ethyl acetate.The mixture was neutralized with saturated aqueous sodium bicarbonate solution., the organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. Then, the resulting residue was subjected to silica gel column chromatography to obtain 15.46 g of 3 -. { 2 -ami non-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (ethoxycarbonyl) methoxypridine. XH-NMR (CDCl3 / 250 MHz) d (ppm): 1.27 (t, 3H, J = 7.1 Hz), 3.5'2 (q, 3H, J = 1.2 Hz), 4.21 (q, 2H, J = 7.1 Hz) ), 4.27 (bs, 2H), 4.9-5.1 (m, 2H), 6.31 (s, 1H), 6.63 (d, 1H, J = 10.9 Hz), 6.79 (d, 1H, J = 6.9 Hz), 6.86 (dd, 1H, J 0 7.8, 4.9 Hz), 7.23 (dd, 1H, J = 7.8, 1.5 Hz), 7.83 (dd, 1H, J = 4.9, 1.5 Hz) Seventh Step A solution of 10.99 g of isoamyl nitrite in 10 ml of acetonitrile was added dropwise to a mixture of 15.46 g of 3-. { 2-amino-4-fluoro-5- [3-methyl-2, β-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-y1] f enox i} -2- (et oxi coal i 1) me t ox ipi idina, 6.19 g of copper chloride (I), 12.61 g of copper (II) chloride and 120 ml of acetonitrile at room temperature, and the mixture stirred for 3 hours. This reaction solution was poured into a mixture of ice and hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 13.16 g of 3-. { 2-chloro-4- f 1'uor o- 5 - [3-methyl-1-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (ethoxycarbonyl) methoxypyridine [compound 7-8 present].
Production Example 9 of the Intermediary: Production of the 3 -. { 2-cl or o- 4-f 1 or o- 5 - [2,6-dioxo-4- (trifluoromethyl) -1,2,6,6-tetrahydropyrimidin-1-yl] phenoxy} - 2 - (methoxycarbonyl) methoxypyridine Step Prime r o In a solution of 227 mg of triphosgene in 8 ml of ethyl acetate, a solution of 155 mg of triethylamine and 250 mg of 4-chloro-2-fluoro-5 was added. { 2- (methoxycarbonyl) methoxy-3-pyroxy loxi} ani 1 ina in 8 ml of ethyl acetate at 0 ° C. The mixture was stirred for 30 minutes at the same temperature, then, for 2 hours at reflux temperature. The reaction solution was filtered while heating, and the solvent was distilled off under reduced pressure to obtain 266 mg of 4-chloro-2-fluoro-5-isocyanate. { 2- (methoxycarbonyl.) Methoxy-3-pyridine loxy} feni lo. Melting point: 113.8 ° C 1 H-NMR (CDC1./300 MHz) d (ppm): 3.76 (s, 3 H), 4.96 (s, 2 H), 6.69 (d, 1 H, J = 7.1 Hz), 6. 93 (dd, 1H, J = 7.8, 5.0 Hz), 7.2-7.3 (m, 2H), 7. 94 (dd, 1H, J = 5.0, 1.4 Hz) The following are prepared in a similar manner: 4-chloro-2-fluoro-5-isocyanate. { 2 - (ethoxycarbonyl) methoxy-3-pyridyloxy} phenyl Isocyanate of 4-chloro-2-f luoro- 5 - [2 -. { 1- (Methoxycarbonyl) ethoxy] -3-pyridyloxy] phenyl. Isocyanate of 4-chlor o-2-luoro-5 - [2 -. { 1 - (ethoxycarbonyl) ethoxy} -3-pyridyloxy} phenyl.
Step Two To a mixture of 1 ml of N, N-dimethylformamide and 26 mg of sodium hydride, a solution of 126 mg of ethyl 3-amino-4,4,4-trifluorocrotonate in 1 ml of N, N-dimethylformamide was added. and the mixture was stirred at 0 ° C. After this, a mixture of 266 mg of 4-chloro-2-fluoro-5-isocyanate was added to the reaction mixture. { 2- (methoxycarbonyl) methoxy-3-pyridyloxy} phenyl and 1 ml / of N, -dimethylformamide at the same temperature, and the mixture was stirred overnight at room temperature. The reaction solution was poured into a mixture of hydrochloric acid and ice water, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 3-. { 2-chloro-4-f luoro-5- [2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (methoxycarbonyl) methoxypyridine.
Production Example 41: Production of compound 10-2 present Step One: To a mixture of 24 g of sodium hydride and 500 ml of tetrahydrofuran, 65 g of benzyl alcohol was added dropwise at room temperature. The mixture was stirred until evolution of the hydrogen, stopped, cooled to -50 ° C, then, 100 g of 3,4-dichloro-1,2,5-thiadiazole was added to the mixture. The mixture was stirred overnight at room temperature, and for 3 hours at reflux temperature. The mixture was concentrated, then poured into hydrochloric acid, extracted with methyl ethyl ether. The organic layer was washed with water, then saturated saline solution, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 33 g of 4-benzyl-1-oxy-3-chloro-1, 2, 5-l iadi a zol (purity: 72%). 1 H-NMR (CDC1./300 MHz) d (ppm): 5.43 (s, 2H), 7.2-7.5 (m, 5H) Step Two To a solution of 0.60 g of 2-chloro-4-fluoro-5- [3-methyl-1-2,6-dioxo-4- (trifluoromethyl) -1, 2, 3, 6- tet rahidropi rimidin-1-il ] f enol and 0.50 g of 4-benzyloxy-3-chloro- 1, 2, 5 - 1 iadia zol in 8 ml of dimethyl sulfoxide, 0.25 g of potassium carbonate was added, and stirred for 30 minutes at 50 ° C, and for 3 hours' at 100 ° C. The reaction solution was poured into dilute hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with water, then saturated saline solution, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.27 g of 4-benzyloxy-3 -. { 2-chloro-4-fluoro-5- [3-methyl-2, β-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy i} - 1, 2, 5 - 1 i adia z ol (purity: 44%) Step Three A solution of 2.5 g of crude product of 4-benzyloxy-3-. { 2-Chloro-4-fluoro-5- [3-methyl-2, β-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -! 2,5-thiadiazole in 20 ml of trifluoroacetic acid was stirred overnight at room temperature. The solution was concentrated, and the residue was subjected to silica gel column chromatography to obtain 0.50 g of 3 -. { 2-gold-4-f luoro-5 - [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -4-hydroxy-1,2,5-thiadiazole. 1H-NMR (CDC13 / 300 MHz) d (ppm): 3.56 (s, 3H), 6.38 (s, 1H), 7.3-7.5 (m, 2H) Step Four: 200 mg of 3 -. { 2-cl or ro-4-f 1 uo r o -5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -4-hydroxy-1,2,5-thiadiazo-1 and 150 mg of methyl 2-bromopropione were dissolved in 10 ml of N, N-dimethylformamide, to this was added 100 mg of potassium carbonate, and the The mixture was stirred for 3 hours at room temperature. This reaction solution was poured into dilute hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with water, then saturated saline solution, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.17 g of 3-. { 2-chloro-4-fluoro-5- [3-met i 1-2, 6-dioxo-4- (trifluoromethyl) -l, 2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -4- [1- (methoxycarbonyl) ethoxy} - 1, 2, 5-thiadiazole [compound 10-2 present] ^? - NMR (CDC1./300 MHz) d ippm): 1.70 (d, 3H, J = 6.9 Hz), 3.55 (s, 3H), 3.79 (s, 3H), 5.31 (q, 1H, J = 6.9 Hz), 6.36 (s, 1H), 7.3-7.5 (m, 2H) Production Example 42: Production of compound 10-7 present 200 mg of 3-. { 2-chloro-4-fluoro-5 - [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3, β-tetrahydropyrimidin-1-yl] phenoxy} 4-hydroxy-1, 2, 5-tiadiazol and 150 mg of methyl bromoacetate were dissolved in 10 ml of N, N-dimethylformamide, to this was added 100 mg of potassium carbonate, and the mixture was stirred by 3 hours at room temperature. This reaction solution was poured into dilute hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with water, then saturated saline solution, dried over anhydrous magnesium sulfate, and concentrated. Then, the resulting residue was washed with hexane to obtain 0.18 g of 3 -. { 2-cio r o- 4-f luo ro- 5 - [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -4- (methoxycarbonyl) methoxy- 1, 2, 5 -thi adiazole [compound 10-7 present]. X H-NMR (CDCl 3/300 MHz) d (ppm): 3.56 (s, 3 H), 3.81 (s, 3 H), 5.01 (s, 2 H), 6.36 (s, 1 H), 7.3-7.5 (m, 2 H) Production Example 43 Production of compound 3-52 present First step To a mixture of 0.098 g of sodium hydride and, N-dimethyl ormamide, 0.829 g of 2-chloro-4-fluoro or 5 - [3-methyl-1, 6-dioxo-4- was added. (trifluoromethyl) -1,2, 3,6-tet rahydropyrimidin-1-y1] phenol and was stirred at room temperature for 2 hours. Then 5-benzylloxy-4-chloropyridine (rendered as follows) was added to the mixture: A mixture of 0.495 g of 5-benzyl-1-oxy-4-pyrimidone and 10 ml of phosphoryl chloride stirred for 30 minutes at reflux temperature, then the mixture was cooled to room temperature, and concentrated. Ice water was added to the residue, extracted with ether and concentrated.), And stirred for 1 hour at room temperature, and for 1 hour at 60-70 ° C. The mixture was poured into saturated ammonium chloride solution, and extracted with ethyl acetate. The organic layer was washed with saturated ammonium chloride solution, water, 20% aqueous potassium carbonate solution, water, hydrochloric acid and saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.959 g of 5-benzyloxy.-4-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy Jpyrimidine. Melting point: 58.ß ° C Second Step: A mixture of 0.959 g of 5-benz-1-ox i -4- (2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) - 1, 2, 3, 6 -tetrahydropyrimidin-1-yl] phenoxy, piperamethione, 10% palladium / carbon and ethyl acetate was stirred for 8 hours at room temperature under a hydrogen atmosphere.The reaction system was purged with nitrogen, then, the reaction solution was filtered through Celite, and the filtrate was concentrated to obtain 0.824 g of 4 -. {2 - c 1 oro-4-fluoro-5- [3-methyl-2,6-dioxo-4 - (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy.) - 5 -hydroxypyrimidin, Melting point: 190.7 ° C Step Three: To a mixture of 32 mg of sodium hydride and N, N-dimethoxylated, 0.35 g of 4 - was added. { 2-C Parroro-4-f luoro- 5 - [3 -me t i 1 -2,6-dioxo-4- (trifluoromethyl) -1,2,6,6-tetrahydropyrimidin-1-yl] phenoxy} 5-hydroxypyridine and stirred at room temperature for 1 hour. Then 0.135 g of methyl 2-bromoproponone was added to the mixture, and it was stirred for 2 hours at room temperature, then for 1 hour at 50 ° C. The mixture was poured into saturated ammonium chloride solution, and extracted with ethyl acetate. The organic layer was washed with saturated ammonium chloride solution and saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to. silica gel column chromatography to obtain 0.319 g of 4-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -5- (1- (methoxycarbonyl) ethoxy.} Pyridine [compound 3-52 present]. 1 H-NMR (CDC1 / 300 MHz) d (ppm): 1.71 (d, 3H, J = 6.8 Hz), 3.57 ( d, 3H, J = 0.9 Hz), 3.78 (s, 3H), 5.01 (q, 1H, J = 6.8 Hz), 6.37 (s, 1H), 7.24 (d, 1H, J = 6.7 Hz), 7.42 ( d, 1H, J = 8.7 Hz), 8.32 (s, 1H), 8.40 (s, 1H) Production Example 44: Production of compound 3-57 present To a mixture of 32 mg of sodium hydride and N, N-dimethoximated, were added 0. 35 g of 4 -. { 2-chloro-4-f luoro-5 - [3-methyl-2, 6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} - 5-Hydroxypyridine and was stirred at room temperature for 1 hour. Then, 0.124 g of methyl bromoacetate was added to the mixture, and it was stirred for 2 hours at room temperature, then for 1 hour at 50 ° C. The mixture was poured into saturated ammonium chloride solution, and extracted with ethyl acetate. The organic layer was washed with saturated ammonium chloride solution and saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.328 g of 4-. { 2-Chloro-4-fl'uoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -5- (methoxycarbonyl) methoxypyrimidine [compound 3-57 present]. Melting point: 62.5 ° C Production Example 45 Production of compound 1-7 present First Step: 2.6 g of 2-cl or o - 4 - f luor o - 5 - [3 -me thi 2 -2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropi rimidin- 1-yl] f nol and 1.7 g of 4-benzyl or i-2-cl or opiim imi were dissolved in 20 ml of N, N-dimethyl-1-formamide, to this solution were added 1.07 g of sodium carbonate. potassium, and the mixture was stirred for 2 hours at 80 ° C. The reaction solution was cooled to room temperature, then, this reaction solution was poured into ice water, and extracted with ethyl acetate. The organic layer was washed with 10% aqueous sodium hydroxide solution, dried over anhydrous magnesium sulfate, and concentrated to obtain 1.6 g of 4-benzyloxy -2-. { 2-chloro-4-fluoro-5- [3-met i 1-2, 6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy Jpyrimidine.
Step S econd: A solution of 1 g of 4-benz 1 ox i -2 -. { 2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-y1] f enox i} The reaction mixture in trifluoroacetic acid was stirred for 2 hours at 70 ° C. This reaction solution was cooled to room temperature, then, poured into water, and filtered to obtain 0.3 g of 2 -. { 2-cl or o-4-f luor o- 5 - [3-methyl-2, 6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy] - 4-hydroxy-pyrimidine.Step Three: 30 mg of sodium hydride were added to a mixture of 0.3 g of 2 -. { 2-chloro or o-4-f luor o -5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} 4-Hydroxypyrimidine, 127 mg of methyl bromoacetate and N, N-dimethyl t-formamide at 0 ° C, then, the mixture was stirred at room temperature. The solution was poured into a mixture of hydrochloric acid and ice water, and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to obtain 0.2 g of 2-. { 2-Chloro-4-fluoro-5- [3-met i 1-2, 6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -4- (methoxycarbonyl) methoxypyrimidine [compound 1-7 present]. XH-NMR (CDCl3 / 300 MHz) d (ppm): 3.56 (d, 3H, J = 1.1 hz), 3.73 (s, 3H), 4.85 (s, 2H), 6.35 (s, 1H), 6.63 (d, 1H, J = 5.6 Hz), 7.18 (d, 1H, J = 6.9 Hz), 7.38 (d, 1H, J = 9.1 Hz), 8.30 (d, 1H, J = 5.7 Hz) Next, some of the present compounds are exemplified in Tables 1 to 10 along with the compound numbers, but they do not limit the scope of the present compound.
[Table 1] Compound of the formula [1-1]: Uabla 2] Compound of the formula [1-2]: Compound No. Z i Z "R3 2-0C? (CH_.}. C0_.H 2-0CH (C-3) C02CH. 2-0CH (CH_) C02-H_CH_ 2-0CH (C¿) C02CH (C- 3.}. "2-OCH (CROCO, CH CH = CH2 2-0CH_C0_H 2-0C__C0_.CH_CHa 2-0C__C0a H (CH)) a 2-0CH2 C02 CR2 CH = CH2 4-OCH (CH_) C02H 4-0CH (-__) - 0_CH3 4-QCH (-_ 3) C0.CH2CH_ 4-OCH (CHs) COaCH (CHa) ß 4-0CH2C02CH2CH3 4-0CHzC02 H (C _.) 2 2-SCH (CH $) C02H 2-SCH (C __) C02CR3 2-SCH (CH.) C02CH2CH3 2-SCH (CH3) C? 2CH (CH3) 2 Table 3] Compound of the formula [1-3] [Table 4] Compound of the formula [1-4]: [Table 5] Compound of the formula [1-5]: 08 [Table 6] Compound of the formula [1-6]: [Table 7] Compound of the formula [1-7]: [Table 8] Compound of the formula [1-8]: [Table 9] Compound of the formula [1-9]: 9] [Table 10] Compound of the formula [1-10]: Next, the formulation examples of the present compounds are explained. In the examples, the present compounds are shown as Compound No. in Tables 1 to 10, and "part (s)" shows "part (s) by weight".
Formulation Example 1 Fifty (50) parts of each of the compounds present 1-1 to 1-7, 2-1 to 2-106, 3-1 to 3-90, 4-1 to 4-94, 5-1 to 5- 75, 6-1 to 6-60, 7-1 to 7-125, 8-1 to 8-42, 9-1 to 9-50, and 10-1 to 10-22, 3 parts of liginsul phona to Calcium, 2 parts of sodium lauryl sulphate, and 45 parts of synthetic hydrated silicon dioxide are well pulverized and mixed, to obtain each of the water miscible powders.
Formulation Example 2 Ten (10) parts of each of the compounds present 1-1 to 1-67, 2-1 to 2-106, 3-1 to 3-90, 4-1 to 4-94, 5-1 to 5- 75, 6-1 to 6-60, 7-1 to 7-125, 8-1 to 8-42, 9-1 to 9-50, and 10-1 to 10-22, 14 parts of polioxiet i lenes tir phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 35 parts of xylene, and 35 parts of cyclohexanone are mixed to obtain each of the emulsifiable cable concentrates.
Formulation Example 3 Two (2) part of each of the compounds present 1-1 to 1-67, 2-1 to 2-106, 3-1 to 3-90, 4-1 to 4-94, 5-1 to 5- 75, 6-1 to 6-60, 7-1 to 7-125, 8-1 to 8-42, 9-1 to 9-50, and 10-1 to 10-22, 2 parts of 'synthetic hydrated silica , 2 parts of 1 gnin sul fonat or calcium, 30 parts of bentonite, and 64 parts of kaolin clay are well pulverized and mixed, and after water is added and kneaded well, it is granulated and dried to obtain each one of the granules.
Formulation Example 4 Twenty-five (25) parts of each of the compounds present 1-1 to 1-67, 2-1 to 2-106, 3-1 to 3-90, 4-1 to 4-94, 5-1 to 5- 75, 6-1 to 6-60, 7-1 to 7-125, 8-1 to 8-42, 9-1 to 9-50, and 10-1 to 10-22, 50 parts of an aqueous solution at 10% vinyl alcohol, and 25 parts of water are mixed, are sprayed with moisture until the average particle diameter is 5 μm or less, to obtain each of the fluids.
Formulation Example 5 Five (5) parts of each of the compounds present 1-1 to 1-67, 2-1 to 2-106, 3-1 to 3-90, 4-1 to 4-94, 5-1 to 5- 75, 6-1 to 6-60, 7-1 to 7-125, 8-1 to 8-42, 9-1 to 9-50, and 10-1 to 10-22, 40 parts of aqueous solution were added to 10% polyvinyl alcohol, and the mixture was emulsified and dispersed until the average diameter was 10 μm or less by the homogenizer. Next, 55 parts of water were added to the resulting mixture to obtain each of the concentrated emulsion.
Test Example 1: Test for foliar field treatment A cylindrical plastic pot that has a diameter of 10 cm and a depth of 10 cm was filled with soil and then the virgin mantle was planted like ivy (Ipomoea hederacea) and alcotán (Abutilón theophras t i). These test plants grew in a greenhouse for 10 days. Then, each of the compounds 1-2, 1-42, 1-45, 1-48, 2-2, 2-7, 2-42, 2-45, 3-2, 3-12, 4-7 , 4-85, 5-12-R, 5-12-S, 5-17, 6-2, 7-2, 7-6, 7-8, 7-12, 7-48, 7- 50, 7 -84, 7-118, 7-119, 7-125, 9-7 9-27, and 9-45 was formulated in an emulsifiable concentrate according to Formulation Example 2 and then diluted with the prescribed c * antity. with water containing a spreading agent and the dilution was sprayed uniformly on the foliage of the test plants with a sprayer at a rate of 1000 liters per hectare. After application, the test plants grew in the greenhouse for 16 days, and the herbicidal activity was determined. As a result, the mantle growth of the virgin leaf such as ivy and 'hobby was completely controlled when compounds 1-2, 1-42, 1-45, 1-48, 2-2, 2-7, 2 -42, 2-45, 3-2, 3-12, 4-7, 4-85, 5-12-R, 5-12-S, 5-17, 6-2, 7-2, 7-6 , 7-8, 7-12, 7-48, 7-50, 7-84, 7-118, 7-119, 7-125, 9-7, 9-27 and 9-45 were applied to the dosage of 125g / ha, respectively.
Test Example 2: Test for the treatment of the earth surface of camp'o A cylindrical plastic pot with a diameter of 10 cm and a depth of 10 cm was filled with soil and then the virgin mantle of the leaf was planted as ivy (Ipomoea hederacea) and alcotán (Abutilón theophrasti). Then, each of compounds 1-2, 1-42, 1-48, 2-2, 2-7, 2-42, 2-45, 3-2, 3-12, 4-7, 4-85 , 5-12-R, 5-12-S, 5-17, 6-2, 7-2, 7-6, 7-8, 7-12, 7-48, 7-50, 7-84 ,, 7-118, 7-119, 7-125, 9-7, 9-27 and 9-45, were formulated in an emulsifiable concentrate according to Formulation Example 2 and then diluted in the prescribed amount with water, and the dilution was uniformly sprayed on the surface of the earth with a sprinkler at a rate of 1000 liters per hectare. After application, the test plants grew in the greenhouse for 19 days, and the herbicidal activity was examined. The mantle growth of the leaf virgin such as ivy- and hobby was completely controlled when compounds 1 -2, 1-42, 1-48, 2-2, 2-7, 2-42, 2-45 , 3-2, 3-12, 4-7, 4-85, 5-12-R, 5-12-S, 5-17, 6-2, 7-2, 7-6, 7-8, 7 -12, 7-48, 7-50, 7-84, 7-118, 7-119, 7-125, 9-7, 9-27 and 9-45, were applied at the dosage of 500g / ha, respectively .
Test Example 3: Test for foliar field treatment A plastic pot that has a long size of 27 cm, a short size of 20 cm and a depth of 7.5 cm was filled with soil and then planted with a virgin mantle like ivy (Ipomoea hederacea) and common thistle (Xanthium pensylvanicum). These test plants grew in a greenhouse for 10 days. Then, in this, a common chelloid (Chenopodium album), chenopodium white of red roots and giant jopo (Setaria faberi) which have been sown and grown for 14 days in a greenhouse in advance. The test plants were further grown in the greenhouse for 8 days. Then, the present compound 1-12 was formulated into an emulsifiable concentrate according to Formulation Example 2 and then diluted in the prescribed amount with water containing a propagation agent and the dilution was sprayed uniformly on the foliage of the Test plants with a sprayer at a rate of 1000 liters per hectare. After the application, the test plants grew in the greenhouse for 25 days, and the herbicidal activity was examined. As a result, the mantle growth of the leaf virgin such as ivy, common thistle, common quelite, red-rooted white chenopodium and giant jopo was completely controlled when compounds 1-12 were applied at the 16 g / ha dosage.
Test Example 4: Test for the treatment of the field land surface A plastic pot that has a long size of 32 cm, a short size of 22 cm and a depth of 8 cm was filled with soil and then sown sesbania hemp (Sesbania exaltata), blackberry grass (Solanum nigrum), alcotán (Abutilon theophras t i), clear water pepper (Polygonum lapat hi f olium), common quelite (Chenopodium album) and giant jopo (Setaria faberi). Then, the present compound 1-12 was formulated into an emulsifiable concentrate according to Formulation Example 2 and then diluted in the prescribed amount with water, and the dilution was sprayed evenly on the surface of the soil with a spray to a speed of 1000 liters per hectare. After application, the test plants grew in the greenhouse for 25 days, and the herbicidal activity was examined. The growth of sesbania hemp, blackberry grass, alphan, light water pepper, common quelite and giant jopo was completely controlled when compound 1-12 was applied at the 250 g / ha dsification.
Test Example 5: Test for foliar field treatment A plastic pot that has a long size of 27 cm, a short size of 20 cm and a depth of 7.5 cm was filled with soil and then the virgin mantle was planted as the 'ivy (Ipomoea hederacea) and common thistle (Xanthium pensylvanicum ). Three days later, pata de gallo grass (Echinochloa crus-galli) was planted in it and grew for 7 days in a greenhouse. Then, in this, a common chelloid (Chenopodium album), white chenopodio of red roots and giant jopo (Setaria faberi) which have been sowed and grown for 14 days in a greenhouse in advance, are transliterated. The test plants were further grown in the greenhouse for 8 days. Then, the present compound 7-7 was formulated into an emulsifiable concentrate according to Formulation Example 2 and then diluted in the prescribed amount with water that. It contains a spreading agent and the dilution was sprayed uniformly on the foliage of the test plants with a sprayer at a rate of 1000 liters per hectare. After application, the test plants grew in the greenhouse for 6 days, and the herbicidal activity was examined. As a result, the mantle growth of the leaf virgin such as ivy, common thistle, houndstooth, common quelite, white-chenished red-root and giant joo was completely controlled when compound 7-7 was applied to the dosage of 16 g / ha. In the following test examples, the herbicidal activity was evaluated in 11 levels with Indices from 0 to 10, that is, designated by the number "0", "1", "2", "3", "4", " 5"," 6"," 7"," 8"," 9"or" 10"where" 0"means that this is no or small difference in the degree of germination or growth between the plants not treated and treated. at the time of examination, and "10" means that the test plants were completely dried or their germination growth was completely inhibited.
T ab l a 1 1 Test Example 6 A plastic pot with a long side of 27 cm, a short side of 19 cm and a depth of 7 cm was filled with soil and then large crabgrass (Digitaria sanguinalis) and giant jopo (Setaria faberi) were planted.
Nine days later, leg of rooster grass (Echinochloa crus-galli) was planted in it and grew for 15 days in a greenhouse. In addition, a plastic pot with a long side of 16.5 cm, a short side of 12 cm and a depth of 7 cm was filled with soil and then sown with wild oats (Avena fatua), and grown for 18 days in a greenhouse. Then, each compound 1-67 and A present was formulated in an emulsifiable concentrate according to Formulation Example 2 and then diluted with the prescribed amount with water containing a propagation agent and the dilution was uniformly sprayed on the foliage of Test plants with a sprayer at the rate of 1000 liters per hectare. After application, the test plants grew in the greenhouse for 4 days, and the herbicidal activity was examined. The results are shown in Table 12 below. (In Table 12, the test plants are shown as follows: Grape hound: B, Large crab: LC, Giant octopus: GF, Wild oats: Table 12 Test Example 7 A plastic pot with a long side of 27 cm, a short side of 19 cm and a depth of 7 cm was filled with soil and then sown with a large crab (Digitaria sanguinalis) and a giant cork (Setaria faberi). Nine days later, leg of rooster grass (Echinochloa crus-galli) was planted in it and grew for 15 days in a greenhouse. In addition, a plastic pot with a long side of 16.5 cm, a short side of 12 cm and a depth of 7 cm was filled with soil, then wild oats (Avena fatua) was planted, and it grew for 18 days in a greenhouse. Then, each compound 1-45 and B present was formulated in an emulsifiable concentrate according to Formulation Example 2 and then diluted in the prescribed amount with water containing a propagation agent and the dilution was uniformly sprayed on the foliage of Test plants with a sprayer at the rate of 1000 liters per hectare. After application, the test plants grew in the greenhouse for 4 days, and the herbicidal activity was examined. The results are shown in Table 13 below. (In Table 13, the test plants are shown as follows: Grape hound: B, Large crab: LC, Giant octopus: GF, Wild oat: W Table 13 Test Example 8 A plastic pot with a long side of 16.5 cm, a short side of 12 cm and a depth of 7 cm was filled with soil and then large crabgrass (Digitaria sanguinalis), giant broom (Setaria faberi) and Johnson grass (Sorghum halepense) were planted. . These test plants grew in a greenhouse for 25 days. Then, each compound 2-52 present and C was formulated in an emulsifiable concentrate according to Formulation Example 2 and then diluted in the prescribed amount with water containing a propagation agent and the dilution was uniformly sprayed on the foliage of the test plants with a sprinkler at a speed of 373 liters per hectare. After application, the test plants grew in the greenhouse for 4 days, and the herbicidal activity was examined. The results are shown in Table 14 below. (In Table 4, the test plants are shown as s igue) Large Garranch: LC, Giant Jopo: GF, Zacate Johnson: J Table 14 The excellent herbicidal effect can be obtained by using the present compound.
It is noted that in relation to this date the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention. Having described the invention as above, the content of the following is claimed as property

Claims (41)

  1. CLAIMS 1. A uracil compound of the formula [I] [characterized in that, Q-R represents a group substituted in R3 of a heterocyclic ring of 5 or 6 elements having one or two nitrogen atoms selected from the group consisting of portions represented by the following formulas (wherein, this heterocyclic ring can be substituted with at least one class of substituent selected from the group consisting of halogen, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms carbon, haloalkenyl of 2 to 6 carbon atoms, alkynyl of 2 to 6 carbon atoms, haloalkynyl of 2 to 6 carbon atoms, Cl to C6 alkoxy Cl to C6 alkyl, alkoxy of 1 to 6 carbon atoms, haloalkoxy of 1 to 6 carbon atoms, Cl to C6 alkoxycarbonyl Cl to C6 alkoxy, Cl to C6 alkoxycarbonyl Cl to C6 alkyl, cyano, hydroxy, mercapto, oxo and thioxo.), Y represents oxygen, sulfur, imino or alkylimino of 1 to 3 atoms of carbon, R1 represents alkyl of 1 to 3 carbon atoms or haloalkyl of 1 to 3 carbon atoms R 'represents alkyl of 1 to 3 carbon atoms, R represents carboxy Cl C6 alkyl, Cl to C6 alkoxycarbonyl Cl to C6 alkyl, Cl to C6 haloalkoxycarbonyl Cl to C6 alkyl, C3 to C6 alkenyloxycarbonyl Cl to C 6 alkyl, C3 to C6 haloalkenyloxycarbonyl Cl to C6 alkyl, C3 to C6 alkynyloxycarboni 1 Cl to C6 alkyl, C3 to C6 haloalkynyloxycarbonyl Cl to C6 alkyl, OR7, SR8 or N (R9) R10, X1 represents halogen, cyano, thiocarbamoyl or nitro, X2 represents hydrogen or halogen. . { wherein each of R7, R8 and R10 independently represent carboxy Cl to Cß alkyl, Cl to C6 alkoxycarbonyl Cl to C6 alkyl, Cl to C6 haloalkoxycarbonyl Cl to C6 alkyl, C3 to C6 alkenyloxycarbonyl Cl to C6 alkyl, C3 to C6 haloalkenyloxycarbonyl Cl a C6 alkyl, C3 to C6 al quiñi 1 oxy carboni 1 Cl a C6 alkyl, C3 a C6 haloalkynyloxycarbonyl Cl a _C 6 alkyl, C3 a C8 cycloalkoxycarbonyl Cl a Cß alkyl, C3 a C8 hal oci cl oa 1 coxi carboni 1 Cl a C3 alkyl, C3 to C8 cycloalkenyloxycarbonyl Cl to Cß alkyl, C3 to C8 halocycloalkenyloxycarbonyl Cl to C6 alkyl, Cl to C6 alkoxycarbonyl Cl to C6 alkoxycarbonyl Cl to C6 alkyl, Cl to C8 alkylannaminoxy carboni 1 Cl to C6 alkyl, phenoxy carboni 1 Cl a C6 alkyl which can be substituted, phenyl Cl to C4 alkoxycarbonyl Cl to C6 alkyl which can be substituted, Cl to Cß to coxy aminocarboni 1 Cl to Cß alkyl, (Cl to Cβ alkoxy) (Cl to C3 alkyl) aminocarbonyl Cl a Cß alkyl, Cl a C6 a 1 qu i 1 minocarboni 1 Cl a Cß alquil or, (Cl to C6 alkyl) Cl to Cβ to the 1 aminocarboni 1 Cl to Cß alkyl, phenyl 1 aminocarboni 1 Cl to Cß alkyl which can be substituted, or phenyl Cl to C4 alkylaminocarbonyl Cl to Cß alkyl which can be substituted , and R9 represents hydrogen or alkyl of 1 to 6 carbon atoms} . ], 2. The uracil compound according to claim 1, characterized in that the heterocyclic ring can be substituted with at least one class of substituent selected from the group consisting of halogen, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms. carbon, alkenyl of 3 to 6 carbon atoms, haloalkenyl of 3 to 6 carbon atoms, alkynyl of 3 to 6 carbon atoms, haloalkynyl of 3 to 6 carbon atoms, Cl to C [alpha] alkoxy Cl to C [beta] alkyl, alkoxy of 1 to 6 carbon atoms, haloalkoxy of 1 to 6 carbon atoms, Cl to C [alpha] alkoxycarbonyl Cl to C [alpha] alkoxy, Cl to C [alpha] alkoxycarbonyl Cl to C [beta] alkyl, cyano, hydroxy, mercapto, oxo and thioxo, R3 represents carboxy Cl to C [beta] alkyl , Cl a C β alkoxycarbonyl Cl a C β alkyl, Cl a C β haloalkoxycarbonyl Cl a C β alkyl, C 3 a C β alkenyloxycarbonyl Cl a C β alkyl, C 3 a C β haloalkenyloxycarbonyl Cl a C β alkyl, C 3 a C β alkyne 1 oxy ca rboni 1 Cl a C alquilo alkyl , C3 to C-haloalkynyloxy rbonyl Cl a Cß alkyl, OR7, SR8 or N (R9) R10. { wherein, each of R7, R8 and R10 independently represent carboxy Cl to Cß alkyl, Cl to Cß alkoxycarbonyl Cl to C 4 alkyl, Cl a Cß haloalkoxycarbonyl Cl to C 4 alkyl, C 3 to C β alkenyloxycarbonyl Cl to C 4 alkyl, C 3 to C 1 haloalkenyloxycarbonyl Cl to C 4 alkyl, f 2 to 4 C to C 4 alkyl. which can be substituted, Cl Cl to C4 alkoxycarbonyl Cl to C4 alkyl which can be substituted, Cl to Cβ alkoxyaminocarbonyl Cl to C4 alkyl, (Cl to Cβ alkoxy) (Cl to C3 alkyl) aminocarbonyl Cl to C4 alkyl, Cl to Cß alkylaminocarbonyl Cl to C4 alkyl, (Cl a, Cß alkyl) Cl to Cβ alkylaminocarbonyl Cl to C4 alkyl, phenylaminocarboni 1 Cl to C4 alkyl which can be substituted, or phenyl Cl to C4 alkylaminocarbonyl Cl to C4 alkyl which can be substituted . and R9 represents hydrogen or alkyl of 1 to 6 carbon atoms. } .3. The uracil compound according to claim 1 or 2, characterized in that the group represented by Q-R3 is any group selected from the group consisting of portions represented by the following formulas: [wherein, R3 is the same as defined in claim 1 or 2, each. of Z1 and Z2 independently represent hydrogen, halogen, alkyl of 1 to 6 carbon atoms, haloalkyl of 1 to 6 carbon atoms, alkenyl of 2 to ß carbon atoms, haloalkenyl of 2 to 6 carbon atoms, alkynyl of 2 to 6 carbon atoms, haloa 1 qu ini 1 or 2 to 6 carbon atoms, Cl a C6 alkoxy Cl a Cß alkyl, alkoxy of 1 to 6 carbon atoms, haloalkoxy of 1 a β carbon atoms, Cl a Cß alkoxycarbonyl Cl to Cß alkoxy or cyano. ] The uracil compound according to any of claims 1 to 3, characterized in that X1 is halogen. 5. The uracil compound according to any of claims 1 to 3, characterized in that X1 is nitro. 6. The uracil compound according to any of claims 1 to 3, characterized in that X1 is chloro. 7. The uracil compound according to any of the rei indications 1 to 6, characterized in that X2 is hydrogen or fluorine. The uracil compound according to any of claims 1 to 3, characterized in that X1 is chlorine and X2 is fluorine. 9. The uracil compound according to any of claims 1 to 8, characterized in that R1 is CF3. 10. The uracil compound according to any of claims 1 to 9, characterized in that R2 is methyl. 11. The uracil compound according to any of claims 1 to 10, characterized in that Y is oxygen or sulfur. 12. The uracil compound according to any of claims 1 to 10, characterized in that Y is oxygen. 13. The uracil compound according to any of claims 1 to 12, characterized in that R3 is OR7, SR8 or N (R9) R10, and R7, R8 and R10 are Cl to Cß alkoxycarbonyl Cl to Cß alkyl, Cl to Cß haloalkoxycarbonyl Cl a C C alkyl, C 3 to C β alkenyloxycarbonyl Cl to C β alkyl, C 3 to C β alkynyloxycarboni 1 Cl to C β alkyl or C 3 to C8 cycloalkoxycarbonyl Cl to C 6 alkyl. 14. The uracil compound according to any of claims 1 to 12, characterized in that R3 is OR7, SR8 or N (R9) R10, and R7, R8 and R10 are Cl a Cβ alkoxycarbonyl Cl to C3 alkyl, Cl to Cß haloalkoxycarbonyl Cl to C3 alkyl or C3 to C8 cycloalkoxycarbonyl Cl to C3 alkyl. 15. The compound of. uracil according to any of the rei indications 1 to 12, characterized in that R3 is OR7 or SR8, and R7 and R8 are Cl a Cß to coxi carboni Ime t i 1 or l-. { (Cl to Cß alkoxy) carbonyl. ethyl. 16. The uracil compound in accordance with either. of claims 1 to 12, characterized in that R3 is OR7 or SR8, and R7 and R8 are methyl carbonyl, ethoxycarbonylmethyl, 1- (methoxycarbonyl) ethyl or 1- (ethoxycarbonyl) ethyl. 17. The uracil compound according to any of claims 1 to 16, characterized in that the group represented by Q-R3 is a group of the following formula: 18. The uracil compound according to any of claims 1 to 16, characterized in that the group represented by Q-R3 is any group selected from the group consisting of portions of the following formula: 19. The uracil compound according to any of claims 1 to 16, characterized in that the group represented by Q-R3 is a group of the following formula: 20. A herbicidal composition characterized in that it comprises as an active ingredient the uracil compound according to any of the rei indications 1 to 19, and an inert carrier or diluent. 21. A method for controlling the weed or weed, characterized in that it comprises applying an effective amount of the uracil compound according to any of claims 1 to 19 to the weed or weed or a place where the weed or weed grows or grows . 22. The use of the uracil compound described in any of claims 1 to 19. 23. A compound of the formula [XXXI] [characterized in that X1, X2, R1, Q-R3 and Y are the same as defined in rei indication i.3. 24. The compound according to claim 23, characterized in that the group represented by Q-R3 is any group selected from the group consisting of portions of the following formula: wherein, X1 is halogen, cyano or nitro, X2 is halogen, Y is oxygen or sulfur, R1 is haloalkyl of 1 to 3 carbon atoms, R3 is OR7, SR8 or N (R9) R10, R7, R8 and R10 are Cl a C 1 alkoxycarbonyl Cl a C β alkyl, Cl a C β haloalkoxycarbonyl Cl a C 6 alkyl, C 3 to C β alkenyloxycarbonyl Cl a C β alkyl, C 3 a C β alkynyloxycarbonyl Cl a C β alkyl or C 3 to C 8 cycloalkoxycarbonyl Cl a C β alkyl, and Z 1 and Z 2 are the same as defined in rei indication 3. 25. The compound according to claim 23, characterized in that X1 is chlorine, X2 is fluorine, Y is oxygen, Q-R3 is the same as defined in claim 3, Z1 and Z2 are hydrogen, R1 is trifluoromethyl, R3 is OR7 or SR8, and R7 and R8 are methoxy ca rbon i lmet i 1, ethoxycarbonylmethyl, 1 - (me t ox i carboni 1) et i 1 or 1 '(ethoxycarbonyl) ethyl. 26. The compound according to claim 24, characterized in that X1 is chlorine, X2 is fluorine, Y is oxygen ,. Z1 and Z2 are hydrogen, R1 is trifluoromethyl, R3 is OR7 or SR8, and R7 and R8 are methyl or carbonylmethoxy, ethoxycarbonylmethyl, 1- (methoxycarbonyl) ethyl or 1 (ethoxycarbonyl) ethyl. 27. A compound of the formula [XXXXXI] [XXXXXI] [characterized in that, X1, X2, Y and Q-R3 are the same as defined in claim 1.]. 28. The compound according to claim 27, characterized in that the group represented by Q-R3 is any group selected from the group consisting of portions of the following formula: N ?? wherein, X1 is halogen, cyano or nitro, X2 is halogen, Y is oxygen or sulfur, R3 is OR7, SR8 or N (R9) R10, R7, R8 and R10 are Cl a Cß a 1 coxi carboni 1 Cl a Cß alkyl, Cl to Cß haloalkoxycarbonyl Cl to Cß alkyl, C 3 to Cß alkenyloxycarbonyl Cl to Cß alkyl, C 3 to Cß to lquin 1 oxycarbonyl 1 Cl to Cß alkyl or C3 to C8 cycloalkoxycarbonyl Cl to Cß alkyl, and Z1 and Z2 are the same as defined in claim 3. 29. The compound according to claim 27, characterized in that X1 is chlorine, X2 is fluorine, Y is oxygen, Q-R3 is the same as defined in claim 3, Z1 and Z2 are hydrogen, R3 is OR7 or SR8, and R7 and R8 are metoxycarbonylmethyl, ethoxycarbonylmethyl, 1- (methoxycarbonyl) ethyl or 1 - (ethoxycarbonyl) et i lo. 30. The compound according to claim 28, characterized in that X1 is chlorine, X is fluorine, is oxygen, Z 'is hydrogen, R- is OR7 SR' and R and R1 are methoxycarbonylmethyl, ethoxycarbonylmethyl, 1 (methoxycarbonyl) ethyl or - (Ethoxy carboni 1) ethyl. 31. A compound according to claim 27, characterized in that it is one selected from the group consisting of 4-chloro-2-fluoro-5-. { 2- (methoxycarbonyl) methoxy-3-pyridyloxy} aniline, 4-chloro-2-fluoro-5-. { 2- (ethoxycarbonyl) methoxy-3-pyridyloxy) aniline, 4-chloro-2-fluoro-5- [2-. { 1- (methoxycarbonyl) ethoxy} -3-pyridyloxy] aniline, 4-chloro-2-fluoro-5- [2 -. { 1- (ethoxycarbonyl) ethoxy} -3-pyridyloxy] aniline, 4-chloro-2-fluoro-5- [4- (methoxycarbonyl) methoxy-2-pyrimidyloxy] aniline, 4-chloro-2-fluoro-5- [4- (ethoxycarbonyl) methoxy -2 -pyrimidyloxy] aniline, 4-chloro-2-fluoro-5- [4-. { 1- (methoxycarbonyl) methoxy} -2-pyrimidyloxy] aniline, and 4-chloro-2-fluoro-5- [4 -. { 1- (ethoxycarbonyl) ethoxy} -2-pyrimidyloxy] aniline. 32. A compound of the formula [XXXXXI] [characterized in that, X1, X2, Y and Q-R3 are the same as defined in claim 1.]. 33. The compound in accordance with • claim 32, characterized in that the group represented by Q-R3 is any group selected from the group consisting of portions of the following formula: wherein, X 1 is halogen, cyano or nitro, X 2 is halogen, Y is oxygen or sulfur, R 3 is OR 7, SR 8 or N (R 9) R 10, R 7, R 8 and R 10 are Cl a C 6 alkoxycarbonyl Cl a C β alkyl, Cl to C 1 Haloalkoxycarbonyl Cl to C 3 alkyl, C 3 to C 2 alkenyloxycarbonyl Cl to C 3 alkyl, C 3 to C 1 alkyloxycarbonyl 1 Cl to C 3 alkyl or C 3 to C 8 cycloalkoxycarbonyl Cl to C 3 alkyl, and Z 1 and Z 2 are the same as defined in the claim 3. 34. The compound according to claim 32, characterized in that X1 is chlorine, X2 is fluorine, Y is oxygen, Q-R3 is the same as defined in claim 3, Z1 and Z2 are hydrogen, R3 is OR7 or SR8, and R7 and R8 are methoxycarbonylmethyl, ethoxycarbonylmethyl, 1- (methoxycarbonyl 1) etyl or 1 - (et oxycarbonyl) et i lo. 35. The compound according to claim 33, characterized in that X1 is chlorine, X2 is fluorine, Y is oxygen, Z1 and Z2 are hydrogen, R3 is OR7 or SR8, and R7 and R8 are methoxycarbonyl ethyl, ethoxycarbonylmethyl, 1- (methoxycarbonyl) ) ethyl or 1 - (e toxi carboni 1) et i lo. 36. A compound according to claim 32, characterized in that it is one selected from the group consisting of 4-chloro-2-fluoro isocyanate. { 2 - (methoxycarbonyl) methoxy-3-pyridyloxy} phenyl, isocyanate of 4-cl oro-2-f luo ro- 5 -. { 2 - (ethoxycarbonyl) methoxy-3-pyridyloxy} phenyl, isocyanate of 4-chlor or-2-f 1-5 - [2 -. { 1- (methoxycarbonyl) ethoxy} -3-pyridyloxy] phenyl, isocyanate of 4-chloro-2-f luoro- 5 - [2 -. { 1- (ethoxycarbonyl) ethoxy} -3-pyridylloxy] phenyl, 4-chloro-2-fluoro-5 - [4 - (methoxycarbonyl) methoxy-2-pyrimidi-loxy] phenyl isocyanate, 4-chloro-2-f-5-chloroisocyanate 5 - [ 4 - (ethoxycarbonyl) methoxy-2-pyrimidi loxy] phenol, isocyanate of 4-chloro-2-f luoro- 5 - [4 -. { 1 - (methoxycarbonyl) methoxy} -2-pyrimidi loxi] phenyl, and isocyanate of 4-chloro-2-fluoro-5- [4 -. { 1 - (ethoxycarbonyl) ethoxy} -2-pyrimidi loxi] phenyl. 37. A compound according to claim 1, characterized in that it is one selected from the group consisting of: 3-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (methoxycarbonyl) methoxypyridine, 3-. { 2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (ethoxycarbonyl) methoxypyridine, 3-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2-. { 1- (methoxycarbonyl) ethoxy} pyridine, 3-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2-. { 1- (ethoxycarbonyl) ethoxy Jpyridine, 2-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -4- (methoxycarbonyl) methoxypyrimidine, 2-. { 2-Chloro-4-fluoro-5- [3-ethyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3, β-tetrahydropyrimidin-1-yl] phenoxy} -4- (ethoxycarbonyl) methoxypyrimidine, 2-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -4 - . { 1- (methoxycarbonyl) ethoxy} pyrimidine, and 2-. { 2-Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -4-. { 1- (ethoxycarbonyl) ethoxyjpyrimidine. 38. A compound according to claim 23, characterized in that it is one selected from the group consisting of: 3-. { 2-chloro-4-fluoro-5- [2,6-dioxo-4-. (trifluoromethyl) -1, 2, 3, 6-tetrahydropyrimidin-1-yl] phenoxy} -2- (methoxycarbonyl) methoxypyridine, 3-. { 2-Chloro-4-fluoro-5- [2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -2- (ethoxycarbonyl) methoxypyridine, 3-. { 2-Chloro-4-fluoro-5- [2,6-dioxo-4- (trifluoromethyl) -1,2,3, β-tetrahydropyrimidin-1-yl] phenoxy} -2-. { 1- (methoxycarbonyl) ethoxyjpyridine, 3-. { 2-chloro-4-fluoro-5- [2,6-dioxo-4-. (trifluoromethyl) -1, 2, 3, 6-tetrahydropyrimidin-1-yl] phenoxy} -2-. { 1- (ethoxycarbonyl) ethoxy} pyridine, 2-. { 2-chloro-4-fluoro-5- [2, 6-dioxo-4- (trifluoromethyl) -1, 2, 3, β-tetrahydropyrimidin-1-yl] phenoxy} -4- (methoxycarbonyl) methoxypyrimidine, 2-. { 2-Chloro-4-fluoro-5- [2,6-dioxo-4- (trifluoromethyl) -1,2,3, β-tetrahydropyrimidin-1-yl] phenoxy} -4- (ethoxycarbonyl) methoxypyrimidine, 2-. { 2-Chloro-4-fluoro-5- [2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -4 - . { 1- (me t oxycarboni 1) ethoxy} p i r imidine, and 2-. { 2-Chloro-4-fluoro-5- [2,6-dioxo-4- Cryfluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} -4-. { l- (ethoxycarbonyl) ethoxyjpyrimidine 39. A compound of the formula [characterized in that, R is the same as defined in claim 1.]. 40. A compound according to claim 39, characterized in that it is one selected from the group consisting of 2- (methoxycarbonyl) methoxy-3-hydroxypyridine, 2- (ethoxycarbonyl) methoxy-3-hydroxypyridine, 2 -. { 1- (methoxycarbonyl) ethoxy} -3-hydroxypyridine, and 2-. { 1- (ethoxycarbonyl) ethoxy} -3-hydroxypyridine. 41. A compound of the formula [characterized in that, R34 is alkoxycarbonyl methyl of 1 to 6 carbon atoms, 1- (alkoxycarbonyl of 1 to 6 carbon atoms) ethyl, haloalkoxycarbonyl methyl of 1 to 6 carbon atoms, 1- (haloalkoxycarbonyl of 1 to 6 carbon atoms) carbon) and ilo, cycloalkoxycarbonyl methyl of 3 to 8 carbon atoms, 1- (cycloalkoxycarbonyl of 3 to 8 carbon atoms) ethyl. ] 3 SUMMARY OF THE INVENTION The present invention relates to a uracil compound of the formula [I]: [wherein, Q-R3 represents a group substituted in R3 of a 5- or 6-membered heterocyclic ring having one or two nitrogen atoms selected from the group consisting of portions represented in the specification (wherein, this heterocyclic ring can be replace with at least one class of substituent, Y represents oxygen, sulfur, imino or alkylimino of 1 to 3 carbon atoms, R1 represents alkyl of 1 to 3 carbon atoms or haloalkyl of 1 to 3 carbon atoms, R2 represents alkyl of 1 to 3 carbon atoms, R3 represents carboxy Cl to Cß alkyl, Cl to Cß < x // m alkoxycarbonyl Cl to Cβ alkyl, OR7, SR8 or N (R9) R10 or the like, X1 represents halogen, cyano, thiocarbamoyl or nitro, X2 represents hydrogen or halogen. . { wherein, each of R7, 'R8 and R10 independently represent carboxy Cl to Cβ alkyl, Cl to Cβ alkoxycarbonyl Cl to Cβ alkyl, Cl to Cß haloalkoxycarbonyl Cl to Cβ alkyl, or the like, and R9 represents hydrogen or alkyl of 1 to 6 carbon atoms. } . ] The present compound has an excellent herbicidal activity. í / nn
MXPA01001317A 2000-02-04 2001-02-02 Uracil compounds and their use. MXPA01001317A (en)

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KR100673344B1 (en) 2007-02-28
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IL167956A (en) 2009-02-11
EP1122244B1 (en) 2004-09-29
US6537948B1 (en) 2003-03-25
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AR078875A2 (en) 2011-12-07
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EP1122244A1 (en) 2001-08-08
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DE60105859T2 (en) 2006-02-02
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